CN1501962A - Azo compound and process of producing the same, amd novel compound and process of producing azo compounds using the same - Google Patents

Azo compound and process of producing the same, amd novel compound and process of producing azo compounds using the same Download PDF

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CN1501962A
CN1501962A CNA028080092A CN02808009A CN1501962A CN 1501962 A CN1501962 A CN 1501962A CN A028080092 A CNA028080092 A CN A028080092A CN 02808009 A CN02808009 A CN 02808009A CN 1501962 A CN1501962 A CN 1501962A
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group
compound
expression
structural formula
aryl
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CN100390235C (en
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藤原淑记
花木直幸
田中成明
大松祯
矢吹嘉治
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Fujifilm Corp
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Priority claimed from JP2002012108A external-priority patent/JP4095807B2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/84—Nitriles
    • C07D213/85—Nitriles in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/48—Two nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/20—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C09B29/0029—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom
    • C09B29/0037—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom containing a five-membered heterocyclic ring with two nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
    • C09B29/3617—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom
    • C09B29/3621—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring
    • C09B29/3639—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring from a pyridine ring containing one or more amino groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
    • C09B29/3665—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic ring with two nitrogen atoms
    • C09B29/3669—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic ring with two nitrogen atoms from a pyrimidine ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B43/00—Preparation of azo dyes from other azo compounds
    • C09B43/11—Preparation of azo dyes from other azo compounds by introducing hydrocarbon radicals or substituted hydrocarbon radicals on primary or secondary amino groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0906—Organic dyes
    • G03G9/091—Azo dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0906—Organic dyes
    • G03G9/0914—Acridine; Azine; Oxazine; Thiazine-;(Xanthene-) dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
    • B41M5/388—Azo dyes

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  • Chemical & Material Sciences (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A compound represented by the following formula (I) or formula (2-I).

Description

Azo-compound and production method thereof, new compound and utilize the method for this producing azo compounds
Technical field
The present invention relates to a kind of new azo-compound and production method thereof and the method that is used for producing the new compound that is suitable for the azo-compound of making dyestuff and utilizes described new compound production azo-compound.
Background technology
The coloured image recording materials have surpassed the black white image recording materials.They have purposes widely, as colour filter and the solid state image sensor in ink-vapor recording, hot tranfer recording, electrophotography, transfer printing type photographic silver halide material, printing-ink, stylus, the indicating meter (as liquid-crystal display and plasma display), as the charge-coupled device (CCD) image sensor.
These coloured image recording materials and colour filter use additive primary or primary subtractive colors to realize panchromatic reproduction or record as tinting material (dyestuff and pigment).
Yet, also do not have at present the absorption characteristic that is suitable for favourable color dub and the tinting material of the fastness of different relatively working conditionss.
Because the ink jet recording materials cost is low, at a high speed, lower noise and be easy to colored record, therefore universal rapidly and further development will be arranged.In principle, ink-vapor recording be divided into continuous processing and as required the method for the use of ink and water, the former ink droplet is continuously ejection, the latter's ink droplet then is to spray according to image information signal.The mechanism that ink droplet forms comprises: by piezoelectric element pressure is applied on the printing ink so that the piezoelectric system of ink droplet ejection; By adding the thermogenesis bubble so that the heating system of ink droplet ejection; Sound system (acoustic system), and the electrostatic system that sucks or spray ink droplet by electrostatic force.Jetted ink comprises: water color ink, oil-based ink and solid ink (fusion).
The tinting material that is used for jetted ink need have: (1) is in printing ink solvent good solubility or dispersiveness, (2) has the ability that forms video high density, (3) gratifying tone, (4) with respect to (NOx for example of reactive gas in light, heat, the environment, oxidizing gas such as ozone, SOx etc.) fastness, (5) to the patience of water or chemical agent, (6) on medium, has good fixation, make feeler (feathering) minimize (7) stability in ink formulations simultaneously, (8) nontoxicity, (9) high purity and (10) cheapness.The tinting material that all above-mentioned requirements are satisfied in acquisition will be very difficult.Particularly, at present have good pinkish red tone in searching always, to oxidizing gas such as ozone the tinting material particularly of the reactive gas in light and the environment with fastness.
The widely used already coupling component that is used for azoic dyestuff comprises: phenols, naphthols and aniline.JP-A-11-209673 (term " JP-A " means " not examining disclosed Japanese patent application " as used herein) and Japanese Patent 3020660 have disclosed the azoic dyestuff by utilizing these coupling components to obtain, and described dyestuff has satisfied tone but photostabilization is poor.Afterwards, Japanese patent application No. 2000-220649 had proposed to have the improved sunproof dyestuff of satisfied color harmony.Yet, aspect the fastness of oxidizing gas (as ozone), making us being not satisfied at all by the document all tinting materials as can be known.
In searching had dyestuff to the satisfied fastness of oxidizing gas (as ozone), the inventor had drawn such idea: as coupling component, and utilize conventional coupling component such as phenols, naphthols and aniline to realize this idea nitrogen-containing heterocycle compound.The azoic dyestuff of being made by amino-pyrazol diazo component and aniline coupling component is disclosed in JP-A-55-161856, JP-A-61-36362, JP-A-61-152768, JP-A-6-145543, JP-A-7-224230, US4,650,861 and 4,301,070, and JP-W-11-504958 (term ＂ JP-W ＂ means ＂ at the disclosed international patent application ＂ of Japanese national phase as used herein).As mentioned above, also there is not a kind of ordinary method can successfully be provided at all gratifying azoic dyestuff in color harmony fastness aspect.The azoic dyestuff that comprises the pyridine coupling component is known, as is disclosed in the following document: JP-A-51-83631, JP-A-49-74718, JP-A-58-101158, JP-B-52-46230 (term " JP-B " means " having examined Japanese patent application " as used herein), EP23309 and German Patent 2719079,2307444,2513949,2525505 and 2832020.And the azoic dyestuff that comprises pyrazoles diazo component and pyridine coupling component is ignorant fully.
The azoic dyestuff of being made up of pyrazoles diazo component and aniline coupling component is according to for example US3,336,285 and 3,639,384 and English Patent 1,566,985 in the method for instruction synthetic.The method of United States Patent (USP) comprises: with 1-alkyl-4-cyano group-5-amino-pyrazol diazotization, carry out linked reaction then, to produce 1-alkyl-4-cyano pyrazole-5-base azo pigment.Yet the diazonium salt that is used for this method is very easily unstable, and this makes and is difficult to obtain highly purified dyestuff by diazotization and coupling (referring to the Dyes and Pigments of Weaver and Shuttleworth, the 3rd volume, the 81st page (1982)) with high yield.Have short wavelength's tone by method synthetic 1-alkyl-3-(second month in a season or the tertiary alkyl)-4-amino-pyrazol-5-based azo dyes that is disclosed among the JP-B-6-19036, and can not be satisfactory as rosaniline dyes.
Above-mentioned English Patent 1,566, the method that proposes in 985 comprises: make 1-alkyl-3-alkyl (or aryl)-4-halo-5-amino-pyrazol and aromatics coupling component stand diazotization and coupled action, and substitute halogen in the 4-position with-CN, with synthetic 1-alkyl-3-alkyl (or aryl)-4-cyano pyrazole-5-based azo dyes.Utilize the heavy metal prussiate, for example CuCN or Zn (CN) 2, this method will be referred to the problems such as purification of wastewater treatment and gained dyestuff.
The convenience and the high yield production method that comprise the azoic dyestuff of pyrazoles diazo component and pyridine coupling component are ignorant.The known The compounds of this invention synthetic method that is applicable to has many shortcomings.In addition, any substituting group is incorporated on the amino by the pyridine moiety of the dye composition of formula of the present invention (I-H1) expression, follows heat to rise, perhaps usually can relate to and make product be difficult to isolating complex reaction system through regular meeting.In addition, still do not know how to make the azoic dyestuff that comprises pyrazoles diazo component and pyridine coupling component with high yield water-solubleization easily.
Summary of the invention
The objective of the invention is:
I) provide the organic compound with specific structure, it can be used for chemistry, agricultural, medicine etc. or intermediate for this reason.
II) provide new dyestuff, it has the excellent absorption characteristic that is suitable for favourable color rendition and enough photostabilization, thermotolerance, wet fastnesss as one of three primary colors, and to the patience of reactive gas in the environment; And provide the production method of described dyestuff;
III) provide coloured composition, said composition provides coloured image, or has the tinting material of excellent color harmony fastness in widespread use, for example is used for the printing ink composition of ink jet printing; Be used for the printing ink sheet that transferred image forms material; The toning agent of electrophotography; The coloured composition that is used for the colour filter of solid state image sensor such as charge coupled device; With the dyeing solution that is used for textiles;
IV) be provided for the ink composite of ink-vapor recording, this ink composite can form the image with satisfied tone, and this image has high photostabilization and to the patience of environment activity gas (particularly ozone); With
V) provide the new compound that is suitable for producing azo-compound, described azo-compound demonstrates excellent color rendition and has the half narrow-wide sharp absorption characteristic of value as tricolor dye; And by using described new compound to produce the method for azo-compound with high yield.
Having good color in searching is in harmonious proportion in the process of dyestuff of fastness, the inventor finds, above-mentioned purpose of the present invention can be by a first aspect of the present invention (this first aspect comprises following 1) to 10)) realize, promptly realize by the production method of the azo-compound with new particular dye skeleton (shown in following structural formula (I)), this compound and the coloured composition that comprises this compound.
1) a kind of compound by formula (I) expression:
R in the formula 1' expression hydrogen atom, alkyl, cycloalkyl, aralkyl, aryl, heterocyclic radical or acyl group, wherein each group all can have substituting group; R 2' expression hydrogen atom, halogen atom or cyano group; R 3' expression hydrogen atom, alkyl, cycloalkyl, aralkyl, thiazolinyl, aryl, heterocyclic radical, carboxyl or sulfo group, wherein, each group all can have substituting group; R 4', R 5', R 6' and R 7' represent hydrogen atom, alkyl, cycloalkyl, aralkyl, thiazolinyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group, carboxyl, sulfo group or formamyl separately, wherein, each group all can have substituting group, and precondition is R 4' and R 5' do not represent hydrogen atom, R simultaneously 6' and R 7' do not represent hydrogen atom simultaneously; And A 1' and A 2' expression-CR=or nitrogen-atoms separately, precondition is A 1' and A 2' do not represent nitrogen-atoms simultaneously, wherein R represents hydrogen atom or substituting group.
2) represent by (I-R1) by a preferred group of the compound of structural formula (I) expression:
Wherein, R 1', R 2', R 4', R 5', R 6', R 7', A 1' and A 2' as above definition; And the R of structural formula (I-R1) 3" expression alkyl, cycloalkyl, aralkyl, thiazolinyl, aryl or heterocyclic radical.
3) compound by structural formula (I-R1) expression preferably includes the compound of being represented by formula (I-R2):
Figure A0280800900142
Wherein, the R in the structural formula (I-R2) 1', R 2', R 3", R 5', R 6', R 7', A 1' and A 2' as definition in the structural formula (I-R1); And the R of structural formula (I-R2) 4" expression replacement or unsubstituted alkyl, replacement or unsubstituted cycloalkyl, replacement or unsubstituted aralkyl, replacement or unsubstituted thiazolinyl, replacement or unsubstituted aryl, replacement or unsubstituted heterocyclic, carboxyl or sulfo group.
4) compound by structural formula (I-R1) expression preferably includes the compound of being represented by formula (I-R3):
Figure A0280800900151
Wherein, the R of structural formula (I-R3) 1', R 2', R 3", R 5', R 6', R 7', A 1' and A 2' as definition in the structural formula (I-R1).
5) compound by structural formula (I-R1) expression preferably includes the compound of being represented by formula (I-R4):
Wherein, R (I-R4) 1', R 2', R 3", A 1' and A 2' as definition in the structural formula (I-R1); And R (I-R4) 4_, R 5", R 6" and R 7" represent hydrogen atom, alkyl, cycloalkyl, aralkyl, thiazolinyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group or formamyl separately.
6) represent by (I-H1) by a preferred group in the compound of structural formula (I) expression:
Wherein, R 1', R 2', P 4', P 5', R 6', R 7', A 1' and A 2' as above definition.
5) preferably represent by the compound of structural formula (I-H1) expression by formula (I-H2):
Wherein, R 1', R 2', R 6', A 1' and A 2' as above definition; And R (I-H2) 5＂ and R 7_ represent alkyl, cycloalkyl, aralkyl, thiazolinyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group, carboxyl, sulfo group or formamyl separately, each of described group all can have substituting group.
8) the present invention also provides the production method of the compound of structural formula (I-R1).One of described method comprises the steps:
(a) amino-pyrazol-derivatives of structural formula (II) expression and diazo reagent are reacted to form diazonium salt:
In the formula, R 1' and R 2' as above definition.
(b) make diazonium salt and the coupling component reaction of representing by structural formula (III), to form compound by formula (I-H1) expression, wherein, R 4', R 5', R 6', R 7', A 1' and A 2' as above the definition and
Figure A0280800900163
(c) compound that makes structural formula (I-H1) expression in the presence of alkali with alkylating reagent, aromatic yl reagent-ing or heteroaryl reagent react (heterylating agent).Other method comprises by cationoid reaction to be introduced water soluble group in the compound of being represented by structural formula (I-R4).
9) 8) method in, cationoid reaction is a sulfonation reaction.
10) the present invention also provides the production method of the compound of structural formula (I-R2) expression.One of described method comprises: make compound by structural formula (I-H1) expression under oxygen free condition with alkylating reagent, aromatic yl reagent-ing or heteroaryl reagent react.Another production method by the compound of structural formula (I-R2) expression comprises the steps:
Make compound and alkylating reagent, aromatic yl reagent-ing or heteroaryl reagent react by structural formula (I-H2) expression, with form the compound represented by structural formula (I-R3) and
Make compound by structural formula (I-R3) expression under oxygen free condition with alkylating reagent, aromatic yl reagent-ing or heteroaryl reagent react.
In addition, in order to obtain to have the dyestuff of satisfactory tone, the inventor studies dye derivate.As SumioTokita at Chemical Seminar 9 ColorChemistry, pp.150-161, instructed among the Maruzen (1982) like that, the influence of the always nucleophobic energy level of tone and molecular vibration or rotational level.Therefore, the minimizing that can be contemplated that the influence that molecular vibration or rotation cause can make absorption band narrower and sharper (having narrower half breadth).
Bright in order to make, must suppress to center on as R 6Or R 7Aryl or the rotation of the key between the nitrogen-atoms in heterocyclic radical and the structural formula (2-I).That is to say, work as R 6And R 7One of be aryl or heterocyclic radical, when another was a substituting group except that hydrogen atom, described aryl or heterocyclic radical were subjected to described substituent sterically hindered effect, so that the rotation of aryl or heterocyclic radical is suppressed.
Work as R 6And R 7One of when being hydrogen atom, aryl or heterocyclic radical must satisfy one of following condition: (i) described group is bonded to nitrogen-atoms (bonding has R on it being close to 6And R 7) the position of carbon atom on substituting group is arranged; Non--covalent linkage the electron pair such on the (ii) above-mentioned position just like nitrogen-atoms.
By any of above-mentioned configuration, as R 6Or R 7Aryl or heterocyclic radical be in the staggered conformation state with respect to pyridine ring, pyrimidine ring or pyrazine plane of a loop, therefore and suppressed rotation.Confirmed in practice already, and utilized the azo-compound of the compound of structural formula (2-I) not have above-mentioned tone problem.
In process,, will obtain better yield in being reflected at the double-deck system of water/organic solvent when azo-compound is dissolved in when maybe carrying out in the reaction system fully by the compound azo-compound of structural formula (2-I).In addition, the inventor also finds, by using hydrochloric acid-Sodium Nitrite, Isopentyl nitrite or nitrosyl-sulfuric acid (environment amenable diazo reagent), can improve the yield that diazo component changes into diazonium salt significantly.Finished the present invention based on these discoveries.
Above-mentioned purpose of the present invention is by comprising following 11)-13) a second aspect of the present invention finish.
11) the invention provides the compound that structural formula (2-I) is represented:
Figure A0280800900181
Wherein, A 1Expression-CR1=or nitrogen-atoms, A 2Expression-CR2=or nitrogen-atoms, precondition are A 1And A 2Do not represent nitrogen-atoms simultaneously; R 6And R 7One of at least expression aryl or heterocyclic radical, another expression hydrogen atom, aliphatic group, aryl, heterocyclic radical, acyl group, carbalkoxy, aryloxy carbonyl, sulphonamide, wherein, each group can have substituting group; G, R 1And R 2Represent hydrogen atom separately; halogen atom; aliphatic group; aryl; heterocyclic radical; cyano group; carboxyl; formamyl; carbalkoxy; aryloxy carbonyl; acyl group; hydroxyl; alkoxyl group; aryloxy; siloxy-; acyloxy; carbamoyloxy; heterocyclic oxy group; alkoxyl group carbonyl oxygen base; aryloxy carbonyl oxygen base; the amino that alkyl or aryl or heterocyclic radical replace; amido; urea groups; sulfamoylamino group; alkoxycarbonyl amino; aryloxycarbonyl amino; alkyl sulfonyl amino; Arenesulfonyl amino; nitro; alkylthio; arylthio; the heterocycle sulfenyl; alkyl sulphonyl; aryl sulfonyl; alkyl sulphinyl; aryl sulfonyl kia; sulfamyl or sulfo group; wherein; each group can have substituting group; precondition is to work as A 1And A 2Expression-CR respectively 1=and-CR 2In=time, G is not the amino of alkyl-replacement; Or R 1And R 6Together, R 6And R 7Form 5-unit or 6-unit ring together respectively.
12) preferably represent by the compound of structural formula (2-I) expression by formula (2-II):
Figure A0280800900191
Wherein, R 1, R 2, R 6And R 7As above definition; And R 4And R 5One of at least expression aryl or heterocyclic radical, and another expression hydrogen atom, aryl, heterocyclic radical, acyl group, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkylsulfonyl and sulfamyl, wherein, by R 1, R 2, R 4, R 5Or R 6The group of expression can have substituting group.
13) the present invention also provides the production method of azo-compound, and this method comprises the compound that makes structural formula (2-I), the compound of preferred structure formula (2-II) and the diazonium salt reaction that is formed by diazo reagent.
Detailed Description Of The Invention
A first aspect of the present invention
According to the present invention, the compound of structural formula (I) preferably includes the compound of structural formula (I-R1) and the compound of structural formula (I-H1).The compound of structural formula (I-R1) preferably includes by (I-R2), (I-R3) and (I-R4) compound of expression.The compound of structural formula (I-H1) preferably includes the compound of formula (I-H2).
In structural formula (I), R 1' expression hydrogen atom, alkyl, cycloalkyl, aralkyl, aryl, heterocyclic radical or acyl group, wherein, each group can have substituting group.
Term ＂ alkyl ＂ comprises the alkyl and the unsubstituted alkyl of replacement.When not replacing, alkyl preferably comprises 1-12 carbon atom, a particularly 1-6 carbon atom.The substituting group of alkyl comprises hydroxyl, alkoxyl group, cyano group, halogen atom and ionic hydrophilic group.The example of alkyl is methyl, ethyl, butyl, sec.-propyl, tert-butyl, hydroxyethyl, methoxy ethyl, cyanoethyl, trifluoromethyl, 3-sulfo-propyl group and 4-sulfo-butyl.
Term ＂ cycloalkyl ＂ comprises the cycloalkyl and the unsubstituted cycloalkyl of replacement.When not replacing, cycloalkyl preferably comprises 5-12 carbon atom.Substituting group on the cycloalkyl comprises the ionic hydrophilic base.The example of cycloalkyl is a cyclohexyl.
Term ＂ aralkyl ＂ comprises the aralkyl and the unsubstituted aralkyl of replacement.When not replacing, aralkyl preferably comprises 7-12 carbon atom.Substituting group on the aralkyl comprises the ionic hydrophilic base.The aralkyl example is phenmethyl and 2-styroyl.
Term ＂ aryl ＂ means aryl replacement or unsubstituted.Aryl preferably has the 6-12 carbon atom.The substituting group of aryl comprises alkyl, alkoxyl group, halogen atom, alkylamino, amido, formamyl, sulfamyl, sulfonamido, hydroxyl, ester group and ionic hydrophilic group.Aryl comprise phenyl, right-tolyl, p-methoxyphenyl, neighbour-chloro-phenyl-and-(3--sulfo-propyl group amino) phenyl.
That term ＂ heterocyclic radical ＂ is used for describing replacement or unsubstituted heterocyclic.Heterocyclic radical is 5-unit or 6-unit preferably.Suitable substituents comprises amido, formamyl, sulfamyl, sulfonamido, hydroxyl, ester group and ionic hydrophilic group on the heterocyclic radical.The example that heterocyclic radical is suitable is 2-pyridyl, 2-thienyl, 2-thiazolyl, 2-[4-morpholinodithio base and 2-furyl.
Term ＂ acyl group ＂ comprises the acyl group and the unsubstituted acyl of replacement.When not replacing, preferably has the acyl group of 1-12 carbon atom.The substituting group that is used for acyl group comprises the ionic hydrophilic base.The example that acyl group is suitable is ethanoyl and benzoyl.
R 2' expression hydrogen atom, halogen atom or cyano group.
R 4', R 5', R 6' and R 7' represent hydrogen atom, alkyl, cycloalkyl, aralkyl, thiazolinyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group, carboxyl, sulfo group or formamyl separately, wherein, each group can have substituting group.
The definition of term " alkyl ", " cycloalkyl ", " aralkyl ", " aryl ", " heterocyclic radical " and " acyl group " with and about R 1The preferable range of ' description is applicable to R 4', R 5', R 6' and R 7'.
Term " thiazolinyl " comprises the thiazolinyl and the unsubstituted thiazolinyl of replacement.When not replacing, preferably has the thiazolinyl of 1-12 carbon atom.The substituting group of thiazolinyl comprises the ionic hydrophilic base.The example of thiazolinyl is vinyl and allyl group.
Alkylsulfonyl comprises alkyl sulphonyl (for example methyl sulphonyl) and aryl sulfonyl (for example benzenesulfonyl).R 4' and R 5' do not represent hydrogen simultaneously.R 6' and R 7' do not represent hydrogen simultaneously yet.
R 3' expression alkyl, cycloalkyl, aralkyl, thiazolinyl, aryl, heterocyclic radical, carboxyl or sulfo group, wherein, each group can have substituting group.The details of these groups and R 4', R 5', R 6' and R 7' described identical.
A 1' and A 2' expression-CR=or nitrogen-atoms separately, precondition is A 1' and A 2' do not represent nitrogen-atoms simultaneously, wherein, R represents hydrogen atom or substituting group.Substituting group on the carbon atom comprises for R 4', R 5', R 6' and R 7' described those groups.
R in the structural formula (I) 1', R 2', R 3', R 4', R 5', R 6', R 7', A 1' and A 2' represented substituent preferred embodiment is as described below.
R 1' be preferably alkyl or aryl.As R 1' alkyl preferably sec.-propyl or tert-butyl.As R 1' aryl phenyl or have substituent phenyl at 2-, 4-or 6-position preferably with respect to pyrazoles nuclear.
R 2' be preferably cyano group.
R 3' be preferably aryl, heterocyclic radical that is replaced by electron-withdrawing group or the heterocyclic radical that is replaced by electron-withdrawing group.Electron-withdrawing group has 0.20 or bigger Hammett ' s substituent constant σ p value, preferred 0.30 or bigger Hammett ' s substituent constant σ p value.The upper limit of σ p value is preferably 1.0.Explain Hammett ' s substituent constant σ p value briefly at this.Hammett ' s rule is the empirical rule that is proposed in nineteen thirty-five by L.P.Hammett, and it attempts to discuss quantitatively substituting group to benzene derivative reaction and equilibrated influence, and is commonly referred to be effectively today.The substituent constant that is used for Hammett ' s rule comprises σ p value and σ m value.At many books commonly used such as J.A.Dean (ed.), Lange ' s Handbook of Chemistry, 12th Ed., McGraw-Hill (1979) and Kagaku-no-ryoiki, Extra No.122, pp.96-103, among the Nankodo (1979), can find these values.In the present invention, different substituting groups will limit or describe according to Hammett ' s substituent constant σ p.As if but this does not also mean that these substituting groups is confined to its σ p value from document those substituting groups as can be known, and described substituting group comprises that its σ p value can not find in the literature but falls into any substituting group of described scope when measuring according to Hammett ' s rule.
σ p value be 0.20 or bigger electron-withdrawing group comprise: acyl group; acyloxy; formamyl; carbalkoxy; aryloxy carbonyl; cyano group; nitro; the dialkyl phosphine acyl group; the diaryl phosphono; the diaryl phosphinyl; alkyl sulphinyl; aryl sulfonyl kia; alkyl sulphonyl; aryl sulfonyl; sulfonyloxy; acetylthio; sulfamyl; thiocyanate groups; thiocarbonyl; haloalkyl; halogenated alkoxy; the halo aryloxy; haloalkyl amino; halogenated alkylthio; heterocyclic radical; halogen atom; azo-group; selenocyanic acid ester group and be 0.20 or the aryl that replaces of bigger electron-withdrawing group with σ p value.Wherein preferably cyano group, nitro and halogen atom.
As previously defined, A 1' and A 2' expression-CR=or nitrogen-atoms separately, precondition is A 1' and A 2' do not represent nitrogen-atoms simultaneously, wherein, R represents hydrogen atom or substituting group.Preferably, for better properties A 1And A 2Be-CR=.
Substituting group on the carbon atom is preferably alkyl, carboxyl, formamyl and the cyano group with 1-3 carbon atom.
R 4', R 5', R 6' and R 7' be preferably separately: hydrogen atom, alkyl, aryl, alkylsulfonyl, acyl group or heterocyclic radical with 1-8 carbon atom.More preferably, they represent alkylsulfonyl, acyl group, aryl or heterocyclic radical separately.R 4' and R 5' do not represent hydrogen simultaneously.R 6' and R 7' do not represent hydrogen simultaneously yet.
When the compound of wishing structural formula (I) when being water miscible, preferably, R 3', R 4', R 5', R 6' and R 7' at least two, particularly at least three have sulfo group or carboxyl.
The compound of structural formula (I-R1) is by method (A) preparation, and it comprises the steps:
(a) amino-pyrazol-derivatives and diazo reagent by structural formula (II) expression are reacted, with the formation diazonium salt,
(b) make diazonium salt and coupling component reaction by structural formula (III) expression, with form by the compound of structural formula (I-H1) expression and
(c) make compound by structural formula (I-H1) expression in the presence of alkali with alkylating reagent, aromatic yl reagent-ing or heteroaryl reagent react.
Or prepare by the method that comprises the steps (B):
By cationoid reaction water soluble group is introduced in the compound of being represented by structural formula (I-R4).
The diazo reagent that is used for the step (a) of method A comprises: the dilute hydrochloric acid solution of Sodium Nitrite, Isopentyl nitrite and nitrosyl-sulfuric acid, the wherein dilute hydrochloric acid solution of preferred Sodium Nitrite.
In the structural formula (III) of the coupling component that is used for method for expressing A step (b), A 1', A 2', R 4', R 5', R 6' and R 7' preferred embodiment and structural formula (I) described those are identical.
Alkylating reagent, aromatic yl reagent-ing or the heteroaryl reagent of step (c) that is used for method A is respectively by structural formula (IV), (V) or (VI) expression.
R-X?????(IV)
Ar-X????(V)
Het-X???(VI)
In structural formula (IV), R represents to replace or unsubstituted alkyl; And X represents halogen atom or OSO 2R ', wherein R represents alkyl or aryl (for example phenyl).
In the structure formula V, Ar represents the phenyl that replaced by electron-withdrawing group, is preferably had 0.20 or the phenyl that replaces of the electron-withdrawing group of bigger Hammett ' s σ p value.
In structural formula (VI), Het represents heterocyclic radical, preferably 2-pyridyl, 2-thienyl, 2-thiazolyl, 2-[4-morpholinodithio base, triazinyl or and 2-furyl.
The alkali that uses in step (c) comprises: organic bases, as diisopropyl ethyl amine; And mineral alkali, as salt of wormwood, yellow soda ash, sodium bicarbonate, saleratus, sodium hydroxide and potassium hydroxide.
The cationoid reaction that can be used for method B comprises: sulfonation reaction, Mannich reaction and Friedel-Crafts reaction, wherein sulfonation reaction preferably.
The oleum, chloro sulfuric acid, sulphur trioxide, amido sulfonic acid etc. that utilize the vitriol oil, 10-60% carry out the sulfonation reaction of the compound of structural formula (I-R4) as containing or not solvent-laden sulphonating agent.Useful solvent comprises acetate, diacetyl oxide, ethyl acetate, diethyl ether, tetracol phenixin and acetonitrile.
Preferably, the compound of structural formula (I-R4) is at R 3", R 4_, R 5", R 6" and R 7" locate to carry out sulfonation.R as structural formula (I-R4) 3", R 4_, R 5", R 6" or R 7" have manyly can carry out the sulfonated response location time, resulting sulfonated compound can be the mixture that has the compound of sulfo group on different positions.In this case, described mixture can comprise: the less important compound that sulfo group is arranged on main compound that sulfo group is arranged on some position of some group and the different positions at described some group, wherein, according to the peak area in the high speed liquid chromatography, the ratio of less important compound is 0.1-20%.The ideal temperature of reaction is-20-50 ℃, and better is-5-30 ℃.The ideal reaction times is 30 minutes to 10 hours, and what more wish is 1-6 hour.
Compound by structural formula (I-R2) expression can prepare by method C or method D.Described method C comprises: the compound of structural formula (I-H1) and alkylating reagent, aromatic yl reagent-ing or heteroaryl reagent are reacted under oxygen free condition; Described method D comprises: make the compound of structural formula (I-H2) and alkylating reagent, aromatic yl reagent-ing or the heteroaryl reagent react compound with preparation structural formula (I-R3), and the compound of structural formula (I-R3) and alkylating reagent, aromatic yl reagent-ing or heteroaryl reagent are reacted under oxygen free condition.The alkylating reagent that is used for method C and D, aromatic yl reagent-ing or heteroaryl reagent are with above-described those are identical.
It is desirable to produce oxygen free condition as nitrogen or argon gas filling reaction system by using rare gas element.Better is with described rare gas element reaction mixture to be carried out bubbling.
By the amino-pyrazol-derivatives of the step that is used for method C (a) of structural formula (II) expression, by for example at US3,336,285, Heterocycles, vol.20, p.519 the instruction among (1983) and the JP-B-6-19036 is synthesized.
By the pyridine coupling component that is used for method A step (a) of structural formula (III) expression, synthesize by the method for describing among for example JP-A-51-83631, JP-A-49-74718 and the JP-B-52-46230.
Azo-compound (azoic dyestuff) by structural formula (I) expression can synthesize by aforesaid method A, B, C and D.Object lesson according to azo-compound of the present invention is as follows, they be illustrative be not to be used for limiting.
Table 1
Figure A0280800900261
Dyestuff R 1R 2R 3
Figure A0280800900262
Table 1 (continuing)
Figure A0280800900271
Dyestuff R 1R 2R 3
Figure A0280800900272
Table 2
Dyestuff R 1R 2R 3R 4
Figure A0280800900282
Table 3
Dyestuff R 1R 2R 3R 4
Figure A0280800900292
Figure A0280800900293
?????-SO 2CH 3???????
Figure A0280800900294
??????-SO 2CH 3????????C 9H 17(t)??????C 9H 17(t)
Figure A0280800900296
?????????H?????????????
????-SO 2CH 3????????
Figure A0280800900299
????C 9H 17(t)
?????????H?????????????
Figure A02808009002911
?????????H?????????????
Table 3 (continuing)
Figure A0280800900301
Dyestuff R 1R 2R 3R 4
Table 3 (continuing)
Dyestuff R 1R 2R 3R 4
Figure A0280800900312
Table 3 (continuing)
Figure A0280800900321
Dyestuff R 1R 2R 3R 4
Figure A0280800900322
Table 3 (continuing)
Dyestuff R 1R 2R 3R 4
Figure A0280800900332
Table 4
Dyestuff R 1R 2R 3R 4R 5R 6R 7R 8
Figure A0280800900342
??????CN??????
Figure A0280800900343
?????H???????CONH 2????SO 2CH 3????
Figure A0280800900344
Figure A0280800900345
??????Br??????
Figure A0280800900346
?????COOEt???H???????? ?????C 9H 17(t)?????COCH 3
Figure A0280800900348
??????SO 2CH 3
Figure A0280800900349
?CONH 2??H???????
Figure A02808009003410
Figure A02808009003411
???????CN??????? ?H???????H??????? ?????SO 2CH 3
???????Br??????? ?H???????CONH 2?????
Figure A02808009003416
Table 5
Figure A0280800900351
Dyestuff R 1R 2R 3
4-1????????CN??????????
4-2????????CN??????????
4-3????????CONH 2??????
4-4????????CONH 2??????
Figure A0280800900355
4-5????????H????????????
Table 6
Figure A0280800900361
Dyestuff R 1R 2R 3R 4
???????CN??????????
Figure A0280800900363
??????CN??????????
Figure A0280800900365
??????????CONH 2?????????COCH 3???????????
?????????H???????????
Figure A0280800900369
????????????COCH 3
Figure A02808009003610
?????????H??????????
Table 7
Dyestuff R 1R 2R 3
Figure A0280800900372
Table 7 (continuing)
Figure A0280800900381
Dyestuff R 1R 2R 3
Figure A0280800900382
Table 8
Dyestuff R 1R 2R 3R 4
Table 8 (continuing)
Figure A0280800900401
Dyestuff R 1R 2R 3R 4
Table 9
Dyestuff R 1R 2R 3R 4
Figure A0280800900412
????????H????????
Figure A0280800900413
???????????H????????
Figure A0280800900415
Figure A0280800900416
???????????CN???????
Azoic dyestuff of the present invention can be used as image recording material, especially for the color image recording material of ink-vapor recording, hot tranfer recording, pressure sensitive recording, electrophotography, transfer printing type photographic silver halide material, printing-ink, stylus etc.Azoic dyestuff of the present invention is specially adapted to ink jet recording materials, transfer printing type photographic silver halide material, hot tranfer recording material and electrophotographic recording material.Highly preferred application is an ink-vapor recording.In addition, described dyestuff also can be used for the colour filter of liquid-crystal display and solid state image sensor (as CCDs), and the dyeing solution that is used for textiles.
Azo-compound of the present invention can have the substituting group through selecting, so that demonstrate the physicals that required application is wished, as solvability and thermal fluidity.Described azo-compound uses to be suitable for the selected form of intended purpose (as solution or dispersion (for example emulsion or suspension)).
By being dissolved and/or be scattered in oleophylic medium or the water medium, azo-compound of the present invention prepares jetted ink.The preferred water-based inks that uses water medium.As long as effect of the present invention is not weakened, as required, ink composite of the present invention can comprise additive.Useful additive comprises: antidesiccant (wetting agent), anti-enzymatic regent (anti-browning agents), emulsion stabilizer, permeate agent, UV light absorber, sanitas, anti-mycotic agent, pH regulator agent, surface tension modifier, defoamer, viscosity modifier, dispersion agent, dispersion stabilizer, rust-preventive agent and sequestrant.These additives are added directly in the water-based inks prescription.When using oil-soluble colourant with the dispersion form, usually these additives are added in the dye dispersion for preparing, perhaps can be added into the oil phase or the aqueous phase of ink formulations.
Antidesiccant preferably is used for preventing because the spray nozzle clogging due to the ink setting.Water-miscible organic solvent with the vapour pressure that is lower than water is preferred antidesiccant.The example of above-mentioned water-miscible organic solvent comprises: polyvalent alcohol, as ethylene glycol, propylene glycol, glycol ether, polyoxyethylene glycol, thiodiglycol, two thiodiglycols, 2-methyl isophthalic acid, ammediol, 1,2,6-hexanetriol, acetylenediol derivative, glycerine and TriMethylolPropane(TMP); The lower alkyl ether of polyvalent alcohol is as glycol monomethyl methyl (or ethyl) ether, diethylidene glycol monomethyl (or ethyl) ether and triethylene glycol list ethyl (or butyl) ether; Heterogeneous ring compound, as 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, 1,3-dimethyl-2-imidazolone and N-ethylmorpholine; Sulfocompound is as the inferior tetramethylene sulfone (sulfolene) of tetramethylene sulfone, methyl-sulphoxide and 3-; Polyfunctional compound is as Pyranton and diethanolamine; And urea derivative.Polyvalent alcohol preferably wherein is as glycerine and glycol ether.Antidesiccant can use separately or be used in combination with two or more.In ink composite, the preferred content of antidesiccant is 10-50 weight %.
The preferred permeate agent that adds is so that help printing ink to infiltrate in the paper.Useful permeate agent comprises alcohols, as ethanol, Virahol, butanols, two (or three) glycol single-butyl ether and 1,2-hexylene glycol; Sodium lauryl sulphate, sodium oleate and nonionic surface active agent.Not cause that feeler (feathering) or print through are as the criterion to determine the content of permeate agent.In ink composite, the permeate agent content of 5-30 weight % will be enough to produce satisfied result.
UV light absorber is used for improving archives stability.Useful UV light absorber comprises: for example be disclosed in the benzotriazole cpd among JP-A-58-185677, JP-A-61-190537, JP-A-2-782, JP-A-5-197075 and the JP-A-9-34057; For example be disclosed in JP-A-46-2784, JP-A-5-194483 and US3, the benzophenone compound in 214,463; For example be disclosed in the styracin compound among JP-B-48-30492, JP-B-56-21141 and the JP-A-10-88106; For example be disclosed in the triaizine compounds among JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621 and the JP-W-8-501291, and the compound that in ResearchDisclosure No.24239, provides.In addition, also can use fluorescigenic compound when absorbing ultraviolet ray, i.e. white dyes is as diphenyl ethylene derivatives and benzoxazoles derivative.
Anti-enzymatic regent (anti-browning agents) is used for improving the stability of archives.Can use the anti-enzymatic regent of various organic or metal complexs.Organic anti-enzymatic regent comprises quinhydrones, alkoxy phenol, dialkoxy phenol, phenols, phenyl amines, amine, indane, chroman, alkoxyl aniline and heterogeneous ring compound.The metal complex anti-enzymatic regent comprises nickel complex and zinc complex.(No.1 7643 at Research Disclosure, VII-I to VII-J), ibid (No.15162), ibid (No.18716, p.650, hurdle, a left side), ibid (No.36544, p.527), ibid (No.307105, p.872) and provided the object lesson of anti-enzymatic regent among the patent No.15162 that as above quotes as proof.At JP-A-62-215272, among the pp.127-137, compound and the described object lesson thereof represented by general formula also are useful.
Useful anti-mycotic agent comprises sodium dehydroacetate, Sodium Benzoate, pyrithione-1-sodium oxide, ethyl p-hydroxybenzoate and 1,2-benzisothiazole-3-ketone and salt thereof.In ink composite, the preferred content of anti-mycotic agent is 0.02-1.00 weight %.
Above-mentioned neutralizing agent (organic bases and mineral alkali) plays the pH regulator agent.In order to improve the stability in storage of printing ink, preferably add the pH regulator agent so that the pH value of ink composite is adjusted to pH6-10, particularly considers in summer and use and be adjusted to 7-10.
Surface tension modifier comprises non-ionic, cationic or anionic surfactant.For inkjet ink composition, preferably it has 20-60mN/m, particularly the surface tension of 25-45mN/m.For inkjet ink composition, preferably it has 30mPas, particularly 20mPas or lower viscosity.
Useful anionic surfactant comprises: soap, alkyl-sulphate, alkylbenzene sulfonate, sulfonated alkyl naphathalene, dialkyl sulfosuccinate succinate, alkyl phosphate salt, naphthene sulfonic acid-formaldehyde condensation products and polyalkylene glycol alkyl vitriol.Useful nonionic surface active agent comprises polyethylene glycol alkyl ether, polyalkylene glycol alkyl allyl ethers, cithrol, sorbitan alcohol fatty acid ester, polyoxyethylene sorbitan alcohol fatty acid ester, polyoxyethylene alkyl amine, glycerol fatty acid ester, ethylene oxide/propylene oxide segmented copolymer and derives from Air Products with trade(brand)name Surfynol; Chemicals, the alkyne diol based surfactants of Inc..The amine oxide type amphoterics, as N, N-dimethyl-N-alkyl amine oxide also is useful.JP-A-59-157636, the tensio-active agent of describing among pp.37-38 and the Research Disclosure, No.308119 (1989) also is useful.
Addible if desired defoamer comprises: fluorochemicals, silicone compounds and sequestrant, and as EDTA.
When azoic dyestuff of the present invention is scattered in the water medium, the preferred technology that adopts is described among JP-A-11-286637 and Japanese patent application No. 2000-78491,2000-80259 and the 2000-62370, and the colored particles that wherein comprises dyestuff and oil-soluble polymers is scattered in the water medium; Perhaps be described among Japanese patent application No. 2000-78454,2000-78491,2000-203856 and the 2000-203857, the dyestuff that wherein is dissolved in the high boiling organic solvent is scattered in the water medium.With reference to above-cited patent disclosure, suitably select the details of dyestuff dispersing method in water medium, and the kind and the consumption of material therefor (oil-soluble polymers, high boiling organic solvent and additive).In addition, also can azoic dyestuff is directly finely divided in water medium.Dispersion agent or tensio-active agent can help to disperse.Suitable diverting device comprises simple agitator, impeller agitator, straight-line type (in-line) agitator, shredder (for example colloidal mill, ball milling, sand mill, attritor, roller crusher or stir grinding machine), ultrasonic agitation device, high-pressure emulsification device or homogenizer (for example, Gaulin homogenizer, Microfluidizer and DeBEE2000).
Except that above-mentioned document, JP-A-5-148436, JP-A-5-295312, JP-A-7-97541, JP-A-7-82515, JP-A-7-118584, JP-A-11-286637 and Japanese patent application No. 2000-87539 also provide and have been applicable to ink jet ink formulations of the present invention for information about.
The water medium that can be used in ink composite of the present invention normally comprise can with the water of water miscibles organic solvent.Useful comprises with water miscibles organic solvent: alcohols, for example methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, the second month in a season-butanols, uncle-butanols, amylalcohol, hexanol, hexalin and phenylcarbinol; Polyvalent alcohol, for example ethylene glycol, glycol ether, triglycol, polyoxyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butyleneglycol, hexylene glycol, pentanediol, glycerine, hexanetriol and thiodiglycol; Diol, derivatives, for example ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, ethylene diacetate, ethylene glycol monomethyl ether acetate, triglycol monomethyl ether, triglycol list ethyl ether and ethyleneglycol monophenylether; Amine, for example thanomin, diethanolamine, trolamine, N methyldiethanol amine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, quadrol, diethylenetriamine, Triethylenetetramine (TETA), polymine, tetramethyl-trimethylene diamine; And other polar solvent, for example methane amide, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, tetramethylene sulfone, 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, N-vinyl-2-Pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolone, acetonitrile and acetone.These solvents can use separately or mix use with two or more.
Inkjet ink composition preferably comprises azo-compound of the present invention, and its concentration is 0.2-10 weight %.Except that described azo-compound, ink composite can also comprise known tinting material.In this case, the total concn of preferred tinting material is in above-mentioned scope.
Inkjet ink composition of the present invention not only is used for forming monochrome image, but also is used for forming full-colour image.For full-colour image, use magenta ink, cyan ink and Yellow ink.Black ink can be used in combination so that carry out the tone adjustment.
Can select the yellow dyes that is used in combination arbitrarily.Useful yellow dyes comprises: aryl or heteroaryl azoic dyestuff, and it has phenols as coupling component, aphthols, phenyl amines, heterogeneous ring compound (for example pyrazolone or pyridone), open chain activity methene compound etc.; Azomethine dyes, it has the open chain activity methene compound as coupling component; Methine dyes, for example a Ben Yajiaji dyestuff and a methyne dyestuff; The quinone dyestuff is as naphthoquinone dyestuff and anthraquinone dye; Quinone phthalein ketone (quinophthalone) dyestuff, nitro-dye, nitroso-dye, acridine dye and dihydroketoacridine dyestuff.
Can at random select the cyan dye that is used in combination.Useful cyan dye comprises: aryl or heteroaryl azoic dyestuff with phenols as coupling component, aphthols, phenyl amines etc.; Azomethine dyes with phenols as coupling component, aphthols, heterogeneous ring compound (for example pyrrolo-triazole) etc.; Polymethin dyes, for example cyanine dyes, oxonol dyestuff and merocyanine dyes; The carbonium dyestuff is as diphenyl methane dye, triphenylmethane dye and xanthene dye; Phthalocyanine pigment; Anthraquinone dye; Indigoide colors; And thioindigo(id)dyes.
Not colorific yellow or cyan dye also are useful before its chromophoric group is partly dissolved.Counter cation in this class dyestuff comprises: inorganic cation, as basic metal or ammonium ion; Organic cation is as pyridinium salt or quaternary ammonium salt; Or have the polymer cation of above-mentioned positively charged ion as local structure.
The black dyes that can be used in combination comprises disazo dyes, trisazo dye, Tetrakisazo dyes and carbon black dispersion.
By providing energy to jetted ink, so that form little ink droplet, make ink droplet jet to known image-recording medium, form image then, carry out ink-vapor recording.Known medium comprises common paper, resin-coated paper (for example being disclosed in the ink jet recording paper among JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153989, JP-A-10-217473, JP-A-10-235995, JP-A-10-337947, JP-A-10-217597 and the JP-A-10-337947), film, electrophotographic paper, cloth, glass, metal and pottery.
The polymer latex compound can be used for imaging, so that give image with gloss, water-repellancy or improved weathering resistance.Before imaging, afterwards or simultaneously, latex compounds is applied on the image-recording medium.In other words, latex compounds may reside in the medium, or in the ink composite, perhaps uses separately with liquid form.For details, can be with reference to Japanese patent application No. 2000-363090,2000-315231,2000-354380,2000-343944,2000-268952,2000-299465 and 2000-297365.
Can comprise usually as the recording paper and the recording film that utilize printing ink of the present invention to carry out ink jet printing: base material and ink-receiver layer, and back coating as required.Base material comprises paper, synthetic paper and plastics film.Paper as base material passes through long mesh paper making machine by following paper pulp, the paper-making technique of cylinder paper machine etc. and preparing: dissolving pulp (for example LBKP or NBKP), mechanical pulp (ground wood pulp (GP) for example, the ground wood pulp (PGW) of pressurization, refiner mechanical slurry (RMP), thermomechanical pulp (TMP), CTMP (CTMP), chemimechanical pulp (CNP) or chemiground wood pulp (CGP)) or used paper pulp (for example deinking slurry (DIP)), it can comprise known additives such as pigment if desired, tackiness agent, sizing agent, sticking agent, cationics, paper strengthening agent etc.Preferably, the thickness of described base material is the 10-250 micron, quantitatively for 10-250 gram/square metre.
Ink-receiver layer or back coating directly are applied on the base material, perhaps after with applying glues such as starch, polyvinyl alcohol, or are applied thereto after forming immovable bed.If desired, on machine rolling press, temperature-gradient rolling press, soft nip rolling press etc., base material is flattened.Preferred substrate is the paper that is pressed with polyolefin film (for example polyethylene), polystyrene, polyethylene terephthalate, polybutene or its multipolymer and plastics film on its upper strata, two sides.In laminating resin, add white pigment (for example titanium dioxide or zinc oxide) or tinting material (for example cobalt blue, ultramarine or Neodymium trioxide) is desirable.
Provide the ink-receiver layer to the base material to comprise pigment, be preferably white pigment and aqueous binders.Useful white pigment comprises: mineral dye, as lime carbonate, kaolin, talcum, clay, diatomite, synthetic soft silica, pure aluminium silicate, Magnesium Silicate q-agent, Calucium Silicate powder, aluminium hydroxide, aluminum oxide, lithopone, zeolite, barium sulfate, calcium sulfate, titanium dioxide, zinc sulphide and zinc carbonate; And pigment dyestuff, as vinylbenzene plastic pigments, vinylformic acid plastic pigments, urea resin and melamine resin.Porous inorganic pigment preferably.The also pigment of high surface area preferably in addition is as the synthetic soft silica.Silicic anhydride that is obtained by dry method and two of moisture silicic acid that obtained by wet method are all available.Moisture silicic acid is particularly preferred.
Useful aqueous binders comprises: water-soluble polymers, as polyvinyl alcohol, silanol-modified polyethylene alcohol, starch, cationic starch, casein, gel, carboxymethyl cellulose, Natvosol, polyvinylpyrrolidone, polyalkylene oxide class and polyalkylene oxide derivative; And aqueous dispersion polymers, as styrene-butadiene latex and ACRYLIC EMULSION.Aqueous binders can use separately or be used in combination with two or more.To the bounding force of pigment with form with regard to the ability of anti-release coating, described tackiness agent is polyvinyl alcohol and silanol-modified polyethylene alcohol preferably with regard to it.
Except that pigment and aqueous binders, ink-receiver layer can also comprise mordant, water-resisting agent, light fastness improving agent, tensio-active agent and other additives.
The mordant that preferably is added into ink-receiver layer is a fixed.Preferably use the polymeric mordant for this reason.At JP-A-48-28325, JP-A-54-74430, JP-A-54-124726, JP-A-55-22766, JP-A-55-142339, JP-A-60-23850, JP-A-60-23851, JP-A-60-23852, JP-A-60-23853, JP-A-60-57836, JP-A-60-60643, JP-A-60-118834, JP-A-60-122940, JP-A-60-122941, JP-A-60-122942, JP-A-60-235134, JP-A-1-161236 and US 2,484,430,2,548,564,3,148,061,3,309,690,4,115,124,4,124,386,4,193,800,4,273,853,4,282,305 and 4, provided the details of useful polymerization mordant in 450,224.In order to obtain the light fastness of high image quality and improvement, particularly preferably be JP-A-1-161236, the polymerization mordant of describing among the pp.212-215.
The water-proof water-proofing agent of image is preferably included: resin cation (R.C.), as polymeric amide-polyamine Epicholorohydrin, polymine, polyamine sulfone, chlorination dimethyldiallylammonium polymkeric substance, cationic-type polyacrylamide and colloided silica.Polymeric amide-polyamine Epicholorohydrin is particularly preferred.In the picture record layer, the preferred cation resin content is from 1-15 weight %, particularly 3-10 weight %.
The light fastness improving agent comprises zinc sulfate, zinc oxide, bulky amine oxidation inhibitor and benzophenone or benzotriazole UV absorbers.Zinc sulfate is specially suitable.
Tensio-active agent in the picture record layer plays coating additive, anti-improving agent, slip improving agent or the static inhibitor peeled off.Useful tensio-active agent is described among JP-A-62-173463 and the JP-A-62-183457.Can use organofluorine compound substitution tables surface-active agent.Preferred hydrophobic organofluorine compound is as fluorine surfactant, oiliness fluorine cpd (for example fluorocarbon oil) and solid fluorine cpd (for example tetrafluoroethylene resin).The details of organofluorine compound is described in JP-B-57-9053 (cols.8-17), among JP-A-61-20994 and the JP-A-62-135826.Other additive that can be added into ink-receiver layer comprises: pigment dispersing agent, thickening material, defoamer, dyestuff, white dyes, sanitas, pH regulator agent, matting agent and solidifying agent.Ink-receiver layer can have individual layer or bilayer structure.
The back coating that provides as required comprises: white pigment, aqueous binders and additive.White pigment comprises: mineral dye, as Calcii Carbonas, water-ground limestone, kaolin, talcum, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulphide, zinc carbonate, stain white, pure aluminium silicate, diatomite, Calucium Silicate powder, Magnesium Silicate q-agent, synthetic soft silica, colloided silica, colloidal alumina, pseudobochmite, aluminium hydroxide, aluminum oxide, lithopone, zeolite, hydrated halloysite, magnesiumcarbonate, magnesium hydroxide; And pigment dyestuff, as vinylbenzene plastic pigments, vinylformic acid plastic pigments, polyethylene, hollow particle, urea resin and melamine resin.
The aqueous binders that can be used in back coating comprises: water-soluble polymers, as vinylbenzene/maleate copolymer, styrene/acrylic salt copolymer, polyvinyl alcohol, silanol-modified polyethylene alcohol, starch, cationic starch, casein, gel, carboxymethyl cellulose, Natvosol and polyvinylpyrrolidone; And aqueous dispersion polymers, as styrene butadiene emulsion and ACRYLIC EMULSION.The additive that can be used for back coating comprises: defoamer, froth suppressor, dyestuff, white dyes, sanitas and water-resisting agent.
Polymer latex can be incorporated in arbitrary layer of the formation ink jet recording paper that comprises back coating or film, so that improve film performance, and for example dimensional stabilizing, anti-curling, anti-blocking and anti-cracking.Relevant details reference JP-A-62-245258, JP-A-62-136648, and JP-A-62-110066.The polymer latex of low Tg (40 ℃ or lower) is added in the layer that comprises mordant, will prevents to break or curl.The polymer latex of high glass transition temperature is added in the back coating, also will will prevent from effectively to curl.
Ink composite according to the present invention is applicable to arbitrary known ink-vapor recording system, the static system that sprays by electrostatic attraction as ink droplet wherein; Wherein use the piezoelectricity system (pressure pulse system) of the vibration pressure of piezoelectric element; Wherein convert the electrical signal to the sound system of acoustic beam, described acoustic beam is applied on the printing ink, and by utilizing radiation pressure ink jet; And wherein by adding the thermogenesis bubble so that spray the hot system of ink droplet.In addition, ink-vapor recording also comprises: wherein spray the system that many lower concentrations that are referred to as light China ink (photoink) carefully drip; Wherein has substantially the same tone but the ink formulations of different concns improves the system of picture quality with many; And the system of utilizing water white transparency printing ink.
A second aspect of the present invention
In structural formula (2-I), A 1Expression-CR 1=or nitrogen-atoms, A 2Expression-CR 2=or nitrogen-atoms, precondition is A 1And A 2Do not represent nitrogen-atoms simultaneously.Preferred A1 and A2 represent respectively-CR1=or-CR2=.
R 6And R 7In one of at least expression aryl or heterocyclic radical, another expression hydrogen atom, aliphatic group, aryl, heterocyclic radical, acyl group, carbalkoxy, aryloxy carbonyl, sulfamyl, wherein, each group can have substituting group.Preferred R 6And R 7In be aryl or heterocyclic radical one of at least, and another is hydrogen atom, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl.More preferably, R 6And R 7In be aryl or heterocyclic radical one of at least, and another is hydrogen atom, aryl, heterocyclic radical, acyl group or aryl sulfonyl.Particularly preferably be R 6And R 7In one of at least expression aryl or heterocyclic radical, another represents hydrogen atom, aryl or heterocyclic radical.Wherein each group can have substituting group.
As R 6And/or R 7Aryl or heterocyclic radical, preferably such group: it has substituting group, perhaps at least one, preferred two with the atom that is connected to the carbon atom adjacency on the amino nitrogen atom on have lone-pair electron.
G, R 1And R 2Represent hydrogen atom separately; halogen atom; aliphatic group; aryl; heterocyclic radical; cyano group; carboxyl; formamyl; carbalkoxy; aryloxy carbonyl; acyl group; hydroxyl; alkoxyl group; aryloxy; siloxy-; acyloxy; carbamoyloxy; heterocyclic oxy group; alkoxyl group carbonyl oxygen base; aryloxy carbonyl oxygen base; alkyl; the amino that aryl or heterocyclic radical replace; amido; urea groups; sulfamoylamino group; alkoxycarbonyl amino; aryloxycarbonyl amino; alkyl sulfonyl amino; Arenesulfonyl amino; nitro; alkylthio; arylthio; the heterocycle sulfenyl; alkyl sulphonyl; aryl sulfonyl; alkyl sulphinyl; aryl sulfonyl kia; sulfamyl or sulfo group; wherein; each group can have substituting group; precondition is to work as A 1And A 2Respectively expression-CR1=and-during CR2=, G is not the amino of alkyl-replacement.
R 1And R 6Together, R 6And R 7Can form 5-unit or 6-unit ring together respectively.
Amino, amido, urea groups, sulfamoylamino group, alkoxycarbonyl amido, aryloxy carbonyl amino, alkylthio, arylthio or heterocycle sulfenyl that G preferably represents hydrogen atom, halogen atom, aliphatic group, aryl, hydroxyl, alkoxyl group, aryloxy, acyloxy, heterocyclic oxy group, replaced by alkyl or aryl or heterocyclic radical.More preferably, G amino or the amido representing hydrogen atom, halogen atom, alkyl, hydroxyl, alkoxyl group, aryloxy, acyloxy, replaced by aryl or heterocyclic radical.Amino or amido that preferred especially G represents hydrogen atom, replaced by aryl or heterocyclic radical.
Preferred R 1And R 2Represent hydrogen atom, alkyl, carbalkoxy, carboxyl, formamyl or cyano group separately.Each of these groups can have substituting group.
R 1, R 2, R 6, R 7Or the substituting group that G had comprises atom (except the hydrogen atom) and top described as R 1And R 2Group.
When the compound of formula (2-I) and the formed azo-compound of the linked reaction between the diazonium salt are water-soluble dye, preferred R 1, R 2, R 6, R 7Has the ionic hydrophilic substituting group with any of G.Suitable ionic hydrophilic base comprises sulfo group, carboxyl and quaternary ammonium group.Carboxyl and sulfo group are more preferred, and wherein sulfo group is particularly preferred.Carboxyl or sulfo group can be the form of salt.Forming the suitable counter ion of salt comprises: alkalimetal ion (for example sodium ion and potassium ion) and organic cation (for example, tetramethyl guanidine ion).
Below will be to by G, R 1And R 2The substituting group of expression is done more detailed description.Term " halogen atom " comprises fluorine atom, chlorine atom and bromine atoms, and wherein suitable is fluorine atom and chlorine atom.
Term ＂ aliphatic group ＂ comprises replacement or unsubstituted alkyl, replacement or unsubstituted thiazolinyl, replacement or unsubstituted alkynyl and replacement or unsubstituted aralkyl.Aliphatic group can have branched structure or ring texture.Aliphatic group preferably comprises 1-20 carbon atom, a particularly 1-16 carbon atom.The aryl moiety of aralkyl is phenyl or naphthyl preferably, more preferably phenyl.The example of alkyl is methyl, ethyl, butyl, sec.-propyl, tert-butyl, hydroxyethyl, methoxy ethyl, cyanoethyl, trifluoromethyl, 3-sulfo-propyl group, 4-sulfo-butyl, cyclohexyl, benzyl, 2-styroyl, vinyl and allyl group.
Term ＂ aryl ＂ comprises aryl replacement or unsubstituted.Aryl is preferably phenyl or naphthyl.Phenyl more preferably.Aryl preferably comprises 6-20 carbon atom, a particularly 6-16 carbon atom.The example that aryl is suitable is: phenyl, right-tolyl, p-methoxyphenyl, neighbour-chloro-phenyl-,-(3-sulfo group propyl group amino) phenyl, 2,6-diethyl phenyl, 2,4,6-trimethylphenyl, 2,6-dimethyl-4-sulfo group phenyl and 2,4-disulfophenyl.
R in (2-II) 4And R 5One of and/or structural formula (2-I) and (2-II) in R 6And R 7One of when being hydrogen atom, another or a plurality of expression aryl or heterocyclic radical.By the aryl of another or a plurality of expressions preferably: substituent phenyl is arranged, at the ortho position as neighbour-chloro-phenyl-, neighbour-(3-sulfo group propyl group amino) phenyl, neighbour-cyano-phenyl, 2,6-diethyl phenyl, 2,4,6-trimethylphenyl, 2,6-dimethyl-4-sulfo group phenyl or 2,4-disulfophenyl.
As used herein term ＂ heterocyclic radical ＂ comprise replacement or unsubstituted heterocyclic, it can have aliphatic ring, aromatic ring or annelated heterocycles.Heterocyclic radical is 5-unit or 6-unit preferably.Suitable substituents comprises on the heterocyclic radical: aliphatic group, halogen atom, alkyl sulphonyl, aryl sulfonyl, acyl group, amido, sulfamyl, formamyl and ionic hydrophilic group.The example that heterocyclic radical is suitable is 2-pyridyl, 2-thienyl, 2-thiazolyl, 2-benzoxazolyl and 2-furyl.
R in structural formula (2-II) 4And R 5One of and/or structural formula (2-I) and (2-II) in R 6And R 7One of when being hydrogen atom, the heterocyclic radical of representing by other group preferably: 2--pyridine base, 2-thienyl, 2-thiazolyl, 2-[4-morpholinodithio base, 2-benzoxazolyl, 2-imidazolyl or 2-indoles thiazolinyl (indolenyl).
Term ＂ formamyl ＂ comprises replacement and unsubstituted formamyl.Suitable substituents comprises alkyl on the formamyl.The example that formamyl is suitable is methylamino formyl radical and formyl-dimethylamino.
Term ＂ carbalkoxy ＂ means carbalkoxy replacement or unsubstituted.When not replacing, carbalkoxy preferably comprises 2-12 carbon atom.Ionic hydrophilic group is a suitable substituents.Ethoxycarbonyl is suitable carbalkoxy.
Term ＂ aryloxy carbonyl ＂ means aryloxy carbonyl replacement or unsubstituted.When not replacing, aryloxy carbonyl preferably has 7-12 carbon atom.Suitable substituents comprises ionic hydrophilic group on the aryloxy carbonyl.Carbobenzoxy is the suitable example of aryloxy carbonyl.
Term ＂ acyl group ＂ comprises the acyl group and the unsubstituted acyl of replacement.When not replacing, the acyl group with 1-12 carbon atom is suitable.Ionic hydrophilic group is a suitable substituents.The example that acyl group is suitable comprises ethanoyl and benzoyl.
Term ＂ alkoxyl group ＂ comprises and replacing or unsubstituted alkoxyl group.When not replacing, the alkoxyl group that comprises the 1-12 carbon atom is suitable.Suitable substituents comprises alkoxyl group, hydroxyl and ionic hydrophilic group on the alkoxyl group.The example that alkoxyl group is suitable is: methoxyl group, oxyethyl group, isopropoxy, methoxy ethoxy, hydroxyl-oxethyl and 3-carboxyl propoxy-.
Term ＂ aryloxy ＂ means aryloxy replacement or unsubstituted.When not replacing, preferably has the aryloxy of 6-12 carbon atom.Suitable substituents comprises alkoxyl group and ionic hydrophilic group on the aryloxy.The example that alkoxyl group is suitable is: phenoxy group, right-methoxyl group phenoxy group and O-methoxy phenoxy group.
Term ＂ acyloxy ＂ means acyloxy replacement or unsubstituted.When not replacing, preferably has the acyloxy of 1-12 carbon atom.The suitable substituents that is used for acyloxy comprises ionic hydrophilic group.The example that acyloxy is suitable is acetoxyl group and benzoyloxy.
Term ＂ carbamoyloxy ＂ comprises replacement and unsubstituted carbamoyloxy.Suitable substituents comprises alkyl on the carbamoyloxy.Suitable carbamoyloxy group comprises N-methylamino methanoyl.
Term ＂ heterocyclic oxy group ＂ means heterocyclic oxy group replacement or unsubstituted.When not replacing, preferably has the heterocyclic oxy group of 1-9 carbon atom.Suitable substituents comprises alkyl and halogen atom on heterocyclic oxy group.Suitable heterocyclic oxy group comprises the 2-pyridyloxy.
Term ＂ alkoxyl group carbonyl oxygen base ＂ represents alkoxyl group carbonyl oxygen base that replace or unsubstituted.When not replacing, preferably has the alkoxyl group carbonyl oxygen base of 2-10 carbon atom.Substituting group on the alkoxyl group carbonyl oxygen base preferably includes alkyl.Alkoxyl group carbonyl oxygen base preferably includes oxyethyl group carbonyl oxygen base.
Term ＂ aryloxy carbonyl oxygen base ＂ represents aryloxy carbonyl oxygen base that replace or unsubstituted.When not replacing, aryloxy carbonyl oxygen base preferably comprises 6-16 carbon atom.Suitable substituents is alkyl and halogen atom on the aryloxy carbonyl oxygen base.Suitable aryloxy carbonyl oxygen base comprises 2-ethyl phenoxy group carbonyl oxygen base.
Term " by the amino of alkyl, aryl or heterocyclic radical replacement " does not comprise unsubstituted amino group.Alkyl, aryl or heterocyclic radical can have substituting group in addition.
That term ＂ alkylamino ＂ means replacement or unsubstituted alkyl amino.When not replacing, preferably has the alkylamino of 1-6 carbon atom.Ionic hydrophilic group is a suitable substituents.The example that alkylamino is suitable is methylamino and diethylamino.
Term ＂ arylamino ＂ represents arylamino that replace or unsubstituted.When not replacing, preferably has the arylamino of 6-12 carbon atom.Suitable substituents comprises halogen atom and ionic hydrophilic group on the arylamino.Suitable arylamino is anilino and 2-chloroanilino.
Term ＂ amido ＂ represents amido that replace or unsubstituted.When not replacing, preferably has the amido of 2-12 carbon atom.Ionic hydrophilic group is a substituent suitable example on the amido.Suitable amido comprises kharophen, propionamido, benzamido, N-phenyl kharophen and 3,5-disulfobenzene formamido group.
Term ＂ urea groups ＂ means urea groups replacement or unsubstituted.When not replacing, preferably has the urea groups of 1-12 carbon atom.Be used for the urea groups suitable substituents and comprise alkyl and aryl.The example that urea groups is suitable is a 3-methyl urea groups, 3,3-dimethyl urea groups and 3-phenyl urea groups.
Term ＂ sulfamoylamino group ＂ represents sulfamoylamino group that replace or unsubstituted.Be used for the sulfamoylamino group suitable substituents and comprise alkyl.Suitable sulfamoylamino group comprises N, N-dipropyl sulfamyl.
Term ＂ alkoxycarbonyl amino ＂ means alkoxycarbonyl amino replacement or unsubstituted.When not replacing, preferably has the alkoxycarbonyl amino of 2-12 carbon atom.Ionic hydrophilic group is a suitable substituents.Alkoxycarbonyl amino comprises ethoxy carbonyl amino.
The amino ＂ of term ＂ aryloxycarbonyl comprises the thiazolinyl and the unsubstituted aryloxycarbonyl amino of replacement.When not replacing, preferably has the aryloxycarbonyl amino of 7-12 carbon atom.Ionic hydrophilic group is a preferred substituted.Phenyloxycarbonyl amino is suitable aryloxycarbonyl amino.
That replacement represents respectively in amino ＂ of term ＂ alkyl sulfonyl and term " Arenesulfonyl amino " or unsubstituted alkyl sulfonamido and replacement or unsubstituted Arenesulfonyl amino.When not replacing, preferably have those groups of 1-12 carbon atom.Be used for alkyl-or aryl-sulfonamido suitable substituents comprise ionic hydrophilic group.Alkyl-or the suitable example of aryl-sulfonamido comprise: methanesulfonamido, N-phenyl methanesulfonamide amido, phenylsulfonamido and 3-carboxyl phenylsulfonamido.
Term " alkylthio ", " arylthio " and " heterocycle sulfenyl " are represented respectively to replace or unsubstituted alkylthio, replacement or unsubstituted arylthio and replacement or unsubstituted heterocycle sulfenyl.When not replacing, preferably contain those groups of 1-12 carbon atom.Suitable substituents comprises the ionic hydrophilic base on these groups.The example of these groups comprises methylthio group and 2-pyridine sulfenyl.
That term ＂ alkyl sulphonyl ＂ and term ＂ aryl sulfonyl ＂ represent respectively to replace or unsubstituted alkyl alkylsulfonyl and replacement or unsubstituted aryl sulfonyl.When not replacing, preferably have those groups of 1-12 carbon atom.Suitable substituents comprises alkyl and ionic hydrophilic group on these groups.The example that these groups are suitable is methylsulfonyl and 4-carboxyl benzenesulfonyl.
That term ＂ alkyl sulphinyl ＂ and term ＂ aryl sulfonyl kia ＂ represent respectively to replace or unsubstituted alkyl sulfinyl and replacement or unsubstituted aryl sulfonyl kia.When not replacing, preferably have those groups of 1-12 carbon atom.Suitable substituents comprises alkyl and phenyl on these groups.The example that alkyl sulphinyl and aryl sulfonyl kia are suitable comprises methanesulfinyl and benzenesulfinyl.
Term ＂ sulfamyl ＂ means sulfamyl replacement or unsubstituted.Alkyl is a suitable substituents.Suitable is that sulfamyl comprises dimethylamino alkylsulfonyl and two-(2-hydroxyethyl) sulfamyl.
In the compound by structural formula (2-I) expression, preferably by those compounds of structural formula (2-II) expression:
Figure A0280800900561
Wherein, R 1, R 2, R 4, R 5, R 6And R 7As above definition.
Preferred R 4And R 5One of be aryl or heterocyclic radical, another is hydrogen atom, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl.More preferred R 4And R 5One of be aryl or heterocyclic radical, and another is hydrogen atom, aryl or heterocyclic radical.By R 6Or R 7The aryl of expression and the preferred embodiment of heterocyclic radical are applicable to by R 4Or R 5Those groups of expression.
In structural formula (2-II), by R 1, R 2, R 4, R 5, R 6And R 7The group of expression can have substituting group.Therefore, suitable substituents is included in the structural formula (2-I) as substituting group G, R 1And R 2Described those groups and ionic hydrophilic group.
Compound by structural formula (2-I) expression preferably has following substituent combination.
(a) R 6And R 7One of expression aryl or heterocyclic radical, another expression hydrogen atom, alkyl, aryl, heterocyclic radical, alkylsulfonyl or acyl group are preferably represented hydrogen atom, aryl, heterocyclic radical or alkylsulfonyl, more preferably represent hydrogen atom, aryl or heterocyclic radical.
(b) G amino or the amido representing hydrogen atom, halogen atom, alkyl, hydroxyl, replaced by aryl or heterocyclic radical, preferred expression hydrogen atom, halogen atom, by amino or amido that aryl or heterocyclic radical replace, amino or the amido more preferably representing hydrogen atom, replaced by aryl or heterocyclic radical.
(c) A 1Expression-CR 1=, A 2Expression-CR 2=, R wherein 1And R 2Represent hydrogen atom, halogen atom, cyano group, formamyl, carboxyl, alkyl, hydroxyl or alkoxyl group separately, preferred hydrogen atom, cyano group, formamyl or alkoxyl group.
By structural formula (2-I) with (2-II) in the compound of expression, preferred wherein said substituting group is selected from one of at least those of above-mentioned atom or group preferably combination; More preferably wherein more a plurality of substituting groups are selected from those of corresponding preferred atom or group; And preferred especially wherein all substituting groups are selected from corresponding preferred atom or group those.
According to the present invention, the production method of azo-compound comprises the compound that makes structural formula (2-I), the compound of preferred structure formula (2-II), and the linked reaction between the diazonium salt that is formed by diazo reagent.Resulting azo-compound is suitable as pigment or dyestuff.
The diazonium salt that can be used for linked reaction preferably includes has amino aromatic substance or heterogeneous ring compound.It is more preferred to have amino heterogeneous ring compound.
The diazo reagent that can be used for forming diazonium salt comprises: the hydrochloric acid soln of Sodium Nitrite, Isopentyl nitrite and nitrosyl-sulfuric acid, the wherein hydrochloric acid soln of preferred Sodium Nitrite.
When carrying out linked reaction, the preferred solvent of structural formula (2-I) and compound (2-II) is a pyridine.
By formula (2-I) and (2-II) object lesson of compound of expression be shown among the table 1-5, described table is merely illustrative and not restrictive.
Table 2-1
Compound R 2R 4R 6R 7
2-1-1???????-CH 3???????
Figure A0280800900582
?????????-H
2-1-2???????-CH 3???????
Figure A0280800900583
??????-H
2-1-3???????-CH 3???????
Figure A0280800900584
2-1-4???????-CH 3???????
Figure A0280800900585
???????????????-H
2-1-5???????-CH 2COOH??? ?????????-H
Table 2-2
Figure A0280800900591
Compound R 2R 4R 6R 7
2-1-6???????-COOH????????
Figure A0280800900592
??????-H
2-1-7???????-CH 3??????? ?????????-H
2-1-8???????-CH 3???????
Figure A0280800900594
????-H
2-1-9???????-CH 3??????? ????????-H
2-1-10??????-CH 3???????
Figure A0280800900596
??????????????-H
Table 2-3
Compound R 2R 4R 6R 7
2-1-11??????-CH 3?????????? ????????-H
2-1-12??????-CH 3??????????
2-1-13??????-CH 2COOK??????
Figure A0280800900604
????????-SO 2CH 3
2-1-14??????-CH 3??????????
2-1-15??????-H??????????????
Figure A0280800900606
Table 2-4
Figure A0280800900611
Compound R 2R 4R 6R 7
2-1-16??????-H???????????
Figure A0280800900612
????-C 3H 6SO 3H
2-1-17??????-COOC 2H 6
2-1-18??????-H???????????
2-1-19??????-CH 3???????
2-1-20??????-CH 3???????
Table 2-5
Figure A0280800900621
Compound R 2R 4R 6R 7
2-1-21??????-CH 3?????????
Figure A0280800900622
????????????-H
2-1-22??????-H???????????
Figure A0280800900623
????-H
2-1-23??????-H?????????????
Figure A0280800900624
????????????-SO 2CH 3
2-1-24??????-Cl????????????
2-1-25??????-Cl????????????
Figure A0280800900626
Embodiment
Now, will make a more detailed description the present invention with reference to synthesis example and embodiment, but should be understood that, the present invention is not intended to be confined to this.Except as otherwise noted, all per-cent and umber are all by weight.
Synthesis example 1
Compound 1-1's is synthetic
Figure A0280800900631
1) compound 1-1a's is synthetic
Under 5 ℃ internal temperature, mixture to the 5-amino-3-tertiary butyl-4-cyano pyrazole (1) of 8 grams (48.7 mmole), 15 milliliters of concentrated hydrochloric acids and 50 ml waters stirs, and in 10 minutes in batches to the Sodium Nitrite that wherein adds 3.36 grams (48.7 mmole).After having added, continue to stir 10 minutes, thereby form diazonium salt.
Respectively, the coupling components (2) of 21.3 grams (40.6 mmole) are packed in the three-necked flask, and to wherein adding 50 gram sodium acetate, 50 milliliters of dimethyl formamides (DMF) and 50 milliliters of ethyl acetate.This mixture stirred and is cooled to 5 ℃ internal temperature.In 10 minutes, diazonium salt is added in the mixture, and continue to stir 30 minutes.The saturated aqueous solution of 300 milliliters of sodium-chlor is added in this reaction mixture.Collect the throw out that so forms by suction filtration, thereby isolate the compound 1-1a of 24.2 grams (85%).
2) compound 1-1's is synthetic
In the compound 1-1a of 28.0 grams (40 mmole), add 8.8 gram (52 mmole) 2-chloro benzothiazoles (heteroaryl reagent 3), 5.5 gram salt of wormwood and 100 milliliters of N,N-DIMETHYLACETAMIDEs (DMAc), and at 100 ℃ to this mixture heating up 1 hour.Reaction is cooled to room temperature with reaction mixture after finishing, and to wherein adding 400 milliliters of saturated aqueous sodium chloride.Collect the throw out that so forms by suction filtration.From acetonitrile, carry out recrystallize obtain 33.3 the gram (80%) compound 1-1.
λ max=545nm (DMF solution)
M/z (positive ion mode)=834
With the compound shown in the synthetic table 10 of the mode identical with synthesis example 1.The result also lists in the table 10.
Table 10
Dyestuff Productive rate (%) λ max (nm) in DMF
????1-2 ????75.2 ??548
????1-3 ????68.3 ??847
????1-4 ????82.5 ??550
????1-5 ????81.1 ??540
????1-6 ????80.5 ??551
????1-7 ????88.7 ??549
????1-8 ????72.3 ??555
????1-9 ????66.9 ??545
????1-10 ????68.3 ??553
????1-11 ????53.8 ??556
????1-12 ????61.2 ??560
????1-13 ????63.3 ??548
????1-14 ????67.3 ??547
????1-15 ????71.1 ??561
????1-16 ????61.3 ??559
????1-17 ????68.2 ??558
Synthesis example 2
Compound 2-1's is synthetic
1) compound 2-1a's is synthetic
Under 5 ℃ internal temperature, 5-amino-3-tertiary butyl-4-cyano pyrazole (1), 15 milliliters of concentrated hydrochloric acids to 8 grams (48.7 mmole), the mixture of 8 milliliters of acetate and 12 milliliters of propionic acid stirs, and in 10 minutes in batches to wherein drip 3.36 the gram (48.7 mmole) the solution of Sodium Nitrite in 10 ml waters.After dripping, continue to stir 30 minutes, thereby form diazonium salt.Respectively, 100 milliliters of pyridines are added in 18.5 gram (40.6 mmole) coupling components (2), then this mixture are stirred and is cooled to 5 ℃ internal temperature.In 30 minutes, diazonium salt is added in the mixture, and continue to stir 30 minutes.The saturated aqueous solution of 300 milliliters of sodium-chlor is added in this reaction mixture.By suction filtration collecting precipitation thing, thereby isolate compound (4-5), output is 17.6 grams (75%).
2) compound 2-1's is synthetic
The 2-chloro benzothiazoles (heteroaryl reagent 3), 5.5 that add 17 grams (100 mmole) in the compound (4-5) of 21.4 grams (40 mmole) restrain salt of wormwood and 100 milliliters of DMAc, and at 110 ℃ to this mixture heating up 4 hours.Reaction is cooled to room temperature with reaction mixture after finishing, and to the saturated aqueous solution that wherein adds 400 milliliters of sodium-chlor.Collect the throw out that so forms by suction filtration.From acetonitrile, carry out recrystallize obtain 15.4 the gram (48%) compound 2-1.
λ max=558nm (DMF solution)
M/z (positive ion mode)=802
With the compound shown in the synthetic table 11 of the mode identical with synthesis example 2.The result also lists in this table.
Table 11
Dyestuff Productive rate (%) λ max (nm) in DMF
????2-2 ????71.3 ??543
????2-3 ????68.2 ??541
????2-4 ????65.4 ??558
????2-5 ????60.3 ??555
????2-6 ????58.3 ??560
????2-7 ????57.3 ??560
????2-8 ????62.3 ??557
????2-9 ????61.1 ??558
????2-10 ????55.5 ??563
????2-11 ????63.3 ??560
????2-12 ????61.8 ??560
????2-13 ????59.3 ??561
????2-14 ????53.2 ??563
????2-15 ????68.2 ??560
????2-16 ????66.3 ??561
Synthesis example 3
Compound 2-1's is synthetic
Compound (2-4) compound (2-1)
In the compound 2-4 of 37.3 grams (56 mmole), add 18.9 gram (112 mmole) 2-chloro benzothiazoles (heteroaryl reagent 3), 20 gram salt of wormwood and 210 milliliters of methyl-sulphoxides (DMSO), and when carrying out bubbling with nitrogen, under agitation in 100 ℃ to this mixture heating up 4 hours.Reaction is cooled to room temperature with reaction mixture after finishing.Collect the throw out that so forms by suction filtration, and the crystallization that obtains is washed with 200 milliliters of DMSO.Crystallization is scattered in 1500 ml waters, filters by suction, water washs then, obtains 29 gram (65%) compound 2-1.
λ max=558nm (DMF solution), m/z (positive ion mode)=802
Synthesis example 4
Compound 6-4's is synthetic
Compound (2-1) compound (6-4)
Pack into 90 milliliter 30% oleum in the three-necked flask and be maintained at about 15 ℃, then in 30 minutes in batches to wherein adding 30 gram (37.5 mmole) compound 2-1.After having added, this mixture is carried out vigorous stirring, under 20 ℃ internal temperature, reacted 5 hours so that make it.This reaction mixture is cooled to 5 ℃, and carefully to wherein dripping 10 ml pure waters, so that make temperature of reaction be no more than 30 ℃.This reaction mixture is dropped to lentamente in the cold saturated aqueous solution of 800 milliliters of sodium-chlor, thus the coarse crystallization of being settled out.Simultaneously, sodium hydroxide concentrated aqueous solutions (NaOH of 70 grams is in 200 milliliters pure water) is dropped in this reaction system.During adding, the internal temperature of system remains on 40 ℃ or lower.Also wash by filtering the collecting precipitation thing with the saturated aqueous solution of 300 milliliters of sodium-chlor.Resulting crude product 6-4 is dissolved in the mixture of 600 ml methanol and ethanol 1/1 (by volume), and in heating, this solution is filtered.In this filtrate, drip the solution of potassium acetate in 120 ml methanol and ethanol 1/1 (by volume) mixture,, filter then so that carry out recrystallize.The crystallization of collecting is carried out desalination by film, so that provide the compound 6-4 of highly purified 35 grams (72.3%).
λmaX＝560nm(DM50)
Synthesis example 5
With the compound shown in the synthetic table 12 of the mode identical with synthesis example 4.Reaction result is also listed in this table.
Table 12
Dyestuff Productive rate (%) λ max (nm) in DMF
????6-1 ????73 ????548
????6-2 ????62 ????550
????6-3 ????61 ????544
????6-4 ????78 ????555
????6-5 ????70 ????556
????6-6 ????65 ????558
????7-1 ????80 ????560
????7-2 ????73 ????562
????7-3 ????75 ????559
????7-4 ????68 ????555
????7-5 ????63 ????558
????7-6 ????75 ????560
????7-7 ????77 ????557
????7-8 ????79 ????560
????7-9 ????78 ????561
????7-10 ????70 ????560
Synthesis example 6
Compound 2-1's is synthetic
1) compound 4-5's is synthetic
Under 5 ℃ internal temperature, mixture to the mixture of the 5-amino-3-tertiary butyl-4-cyano pyrazole (1) of 7.55 grams (46 mmole), 15 milliliters of concentrated hydrochloric acids and 20 milliliters of acetate and propionic acid 2/3 (by volume) stirs, and in 10 minutes in batches to the solution of Sodium Nitrite in 10 ml waters that wherein drips 3.36 grams (48 mmole).After dripping, continue to stir 10 minutes, thereby form diazonium salt.
Respectively, 100 milliliters of pyridines are added in 20.0 grams (44 mmole) coupling components (2) in three-necked flask, then this mixture are stirred and is cooled to 5 ℃ internal temperature.In 10 minutes, diazonium salt is added in this three-necked flask.After mixture was stirred 30 minutes, the aqueous hydrochloric acid and 600 of this reaction mixture being poured into 110 milliliters of 1N restrained in the mixture of ice.By suction filtration collecting precipitation thing, thus isolate 26.2 the gram (88%) compound 4-5.
2) compound 2-1's is synthetic
In the compound 4-5 of 30.0 grams (56 mmole), add 58.4 milliliters of (224 mmole) 2-chloro benzothiazoles (heteroaryl reagent 3), 62 gram salt of wormwood and 210 milliliters of DMSO, and when carrying out bubbling, this mixture was stirred 4 hours in 100 ℃ with nitrogen.Reaction makes this reaction mixture be cooled to room temperature after finishing.Collect the throw out that so forms by suction filtration, and wash with 200 milliliters of DMSO.Crystallization is scattered in 1500 ml waters, filters by suction, water washs then, to provide 63 gram (80%) compound 2-1.
λ max=558nm (DMF solution), m/z (positive ion mode)=802
With the mode synthetic compound 2-1 identical with top description, different is not carry out nitrogen bubble.As a result, yield is 45%.
Synthesis example 7
Compound 2-1's is synthetic
In the compound 2-4 of 37.3 grams (56 mmole), add 18.9 grams ((112 mmole) 2-chloro benzothiazole (heteroaryl reagent 3), 20 gram salt of wormwood and 210 milliliters of DMSO, and when carrying out bubbling, this mixture was stirred 4 hours in 100 ℃ with nitrogen.Reaction makes this reaction mixture be cooled to room temperature after finishing.Collect the throw out that so forms by suction filtration, and wash with 200 milliliters of DMSO.Crystallization is scattered in 1500 ml waters, filters by suction, water washs then, to provide 29 gram (65%) compound 2-1.
λ max=558nm (DMF solution), m/z (positive ion mode)=802
With with top described identical mode synthetic compound 2-1, different is not carry out nitrogen bubble.As a result, yield is 50%.
Synthesis example 6 and 7 result show: the reaction under oxygen-free atmosphere will obtain better result aspect yield.
Embodiment 1
The preparation of water-based inks
Following component is mixed, stir down, and pressure filtration is the miniature filter for molten of 47 millimeters of 0.8 micron and diameters by mean pore size 30-40 ℃ of heating 1 hour, thus preparation ink composite A.
The prescription of ink composite A:
5 parts of compound 2-13
9 parts of glycol ethers
9 parts of Tetraglycol 99 single-butyl ethers
7 parts of glycerine
2 parts of diethanolamine
70 parts in water
Prepare ink composite B-H with the mode identical with ink composite A, different is, with the dyestuff alternative compounds 2-13 that lists in the following table 13.
Picture record and assessment
By utilizing every kind of ink composite A-H, with the photograph glossy paper of picture record on ink jet printing head (PM-700C derives from Seiko Epson Corp.) (superfine photograph grade derives from Fuji photo Film Co., Ltd.) on.With regard to tone, light fastness and ozone resistants, the image that obtains is carried out following assessment.The results are shown in Table 13.
1) tone
Tone and by the A-C classification detects by an unaided eye.A is " outstanding ", and B is " well ", and C is " poor ".
2) light fastness
Measure density of image (initial density: Ci) with reflection densitometer X-Rite 310TR immediately after the record.Making image be exposed to xenon light in weather-o-meter (Atlas Ci65 derives from Atlas Electric Devices Co.) (in (85,000 lux) after 7 days, is that three points of 1,1.5 and 2.0 are measured density of image (C once more in initial density f).Calculate dyestuff retention (%) by equation:
Dyestuff retention (%)=[(C i-C f)/C i] * 100
Each measurement point dyestuff retention be 80% or higher image be chosen as the A level.At one or two of three measurement point, the dyestuff retention is lower than 80% image and is chosen as the B level.All be lower than 80% image at each measurement point dyestuff retention and be chosen as the C level.
3) ozone resistants
It is the chamber 24 hours of 0.5ppm that recording picture is placed concentration of ozone gas.With with assessment light fastness identical mode, obtain to be exposed to the dyestuff retention after the ozone.(OZG-EM-01 derives from Applics Co., Ltd.) sets the ozone concn in the described chamber to utilize the ozone gas monitor.Each measurement point dyestuff retention be 70% or higher image be chosen as the A level.At one or two of three measurement point, the dyestuff retention is lower than 70% image and is chosen as the B level.All be lower than 70% image at each measurement point dyestuff retention and be chosen as the C level.
Table 13
Printing ink Dyestuff Tone Light fastness Ozone resistants Explain
????A ????2-13 ????A ??A ??A The present invention
????B ????2-14 ????A ??A ??A The present invention
????C ????2-15 ????A ??A ??A The present invention
????D ????2-16 ????A ??A ??A The present invention
????E ????(a) ????A-B ??C ??C Comparative dye
????F ????(b) ????B-C ??B ??C Comparative dye
????G ????(c) ????B ??B ??B Comparative dye
????H ????(d) ????A-B ??A-B ??C Comparative dye
Comparative dye (a)
Figure A0280800900771
Comparative dye (b)
Comparative dye (c)
Comparative dye (d)
Figure A0280800900782
As can be seen from Table 13, more more clear with the magenta color image of ink composite A-D printing than the magenta color image that prints with ink composite E-H.In addition, the image with ink composite A-D printing is being excellent aspect the light fastness.
In addition, by utilizing ink composite A-D, superfine glossy paper (MJA4S3P derives from Seiko Epson) is printed with identical ink-jet printer (PM-700C derives from Seiko Epson).Assessment to the color harmony light fastness of gained image has provided the gratifying result who is similar to table 13.
Embodiment 2
The preparation of ink samples 101
At 70 ℃, the dioctyl sodium sulfo-succinates of azo-compound 2-8 (oil soluble) (5.63 gram) and 7.04 grams are dissolved in the mixture of ethyl acetate of high boiling organic solvent S-2 (seeing below), the 5.63 high boiling organic solvent 5-11 (seeing below) that restrain of 4.22 grams and 50 milliliters.With in the magnetic stirrer, in this solution, add 500 ml deionized water to prepare oil-in-water coarse dispersion, under the pressure of 600 crust, make coarse dispersion pass through Microfluidizer (deriving from Microfluidics Inc.) five times.Utilize rotatory evaporator from resulting emulsion, to remove and desolvate, till the smell of imperceptible ethyl acetate.Fine emulsion and 140 gram glycol ethers, 50 gram glycerine, the 7 gram Surfynol 465 of resulting hydrophobic dye (are derived from Air products ﹠amp; Chemicals Inc.) mixes with 900 ml deionized water, with preparation ink samples 101.
The preparation of ink samples 102-105
Prepare ink samples 102-105 with the mode identical with ink samples 101, different is to substitute oil-soluble compounds 2-8 with the oil-soluble compounds of listing in the following table 14.Utilize ultra-fine grain diameter analyser Microtrack UPA (to derive from Nikkiso Co., Ltd.) measure the volume average particle sizes of sample emulsion.The results are shown in Table 14 for gained.
Picture record and assessment
By utilizing ink samples 101-105 and each of comparative ink composition E-H of preparation in embodiment 1, with picture record at ink jet printing head (PM-700C, derive from Seiko Epson) on photograph glossy paper (ink jetting paper photograph grade, derive from Fuji photo Film Co., Ltd.) on.According to following method, the image of record is assessed with regard to tone, paper independence, water-repellancy, light fastness and ozone resistants.The results are shown in Table 15 for gained.
1) tone
With the wavelength interval of 10nm, in the 390-730nm scope, measure the reflection spectrum of image, and according to CIE 1976 L *a *b *Color space system computing a *And b *Value.Preferred magenta is set up adopted as follows.
Preferred a *Value: 76 or bigger
Preferred b *Value :-30 to 0
A:a *And b *Value is all in corresponding preferable range.
B:a *And b *One of value is in its preferred range.
C:a *And b *Value is all outside corresponding preferable range.
2) paper dependency
Tone to the image that forms on paper at plain paper copier (PPC) at the color harmony of the image that forms on the photograph glossy paper compares.Difference is chosen as the A level for a short time between the two, and this shows little paper dependency; And the big words of difference are chosen as B level (poor).
3) water-repellancy
At room temperature, the photograph glossy paper that is formed with image on it is carried out drying 1 hour, in water, soaked for 30 seconds then, carry out seasoning in room temperature again.Observe the feeler (feathering) of printing ink image, and the water-repellancy of printing ink is chosen as A level (no feeler), B level (slight feeler) or C level (a large amount of feeler).
4) light fastness
In weather-o-meter (deriving from the Ci65 of Atlas), will be exposed to xenon light (in (85,000 lux) 3 days at the image that forms on the photograph glossy paper.Obtain the dyestuff retention with the mode identical with embodiment 1.Each measurement point dyestuff retention be 70% or higher image be chosen as the A level.At one or two of three measurement point, the dyestuff retention is lower than 70% image and is chosen as the B level.All be lower than 70% image at each measurement point dyestuff retention and be chosen as the C level.
The 5} ozone resistants
Use with embodiment 1 in identical testing method and staging hierarchy.
Table 14
Sample Dyestuff Median size (nm)
????101 ????2-8 ????55
????102 ????2-9 ????48
????103 ????2-10 ????63
????104 ????2-11 ????58
????105 ????2-12 ????70
Table 15
Sample Tone Paper independence Water-repellancy Light fastness Ozone resistants
????101 ????A ??A ????A ??A ??A
????102 ????A ??A ????A ??A ??A
????103 ????A ??A ????A ??A ??A
????104 ????A ??A ????A ??A ??A
????105 ????A ??A ????A ??A ??A
????E ????A-B ??B ????B ??B ??C
????F ????B ??B ????B ??A-B ??C
????G ????B ??B ????B ??B ??C
????H ????A-B ??B ????B ??A-B ??C
By the result of table 15 as can be seen, inkjet ink composition according to the present invention is being excellent aspect tone, paper independence, water-repellancy and the light fastness.
Embodiment 3
The ink jet printing head BJ-F850 (deriving from Canon Inc.) that the print cartridge of each ink composite of preparation among the embodiment 2 is equipped with in utilization carries out ink jet printing on photograph glossy paper GP-301 (deriving from Canon Inc.).The assessment result of image is the same satisfactory with the result of acquisition among the embodiment 2.
Embodiment 4
The preparation of water-based inks
Distilled water is added in the mixture of following component, only is upgraded to until reaching 1, and this mixture was stirred 1 hour at 30-40 ℃.If desired, with the potassium hydroxide aqueous solution of 10 mol the pH value of mixture is adjusted to 9.Under the decompression, it is little filter for molten of 0.25 micron that mixture is filtered by mean pore size, thereby prepares magenta ink composition I.
The prescription of ink composite I:
Azo-compound 2-17 8.5 grams per liters
Glycol ether 150 grams per liters
Urea 37 grams per liters
Glycerine 130 grams per liters
Triglycol single-butyl ether 130 grams per liters
Trolamine 6.9 grams per liters
Benzotriazole 0.08 gram/l
Surfynol465 10 grams per liters
Proxel XL2 3.5 grams per liters
Prepare ink composite J-P with the mode identical with ink composite I, different is, with the compound alternative compounds 2-17 that lists in the following table 16.The dyestuff that uses among the comparative dye (a) and (b) of listing in the table 16, (c) and (d) and the embodiment 1 is identical.
Picture record and assessment
Each the ink jet printing head PM-670C (deriving from Seiko Epson) of print cartridge that the ink composite I-P for preparing above is equipped with in utilization carries out ink jet printing on photograph glossy paper EX (deriving from Fuji photo Film).With regard to tone, paper independence, water-repellancy, light fastness and ozone resistants, image is carried out following assessment.The results are shown in Table 16 for gained.
1) tone
Assess and classification with the mode identical with embodiment 1.
2) paper independence
Assess and classification with the mode identical with embodiment 2.
3) water-repellancy
At room temperature, the photograph glossy paper of the image that is formed with reflection density about 1.0 on it is carried out drying 1 hour, in ion-exchanged water, soaked 3 minutes seasoning at room temperature more then.According to the water-repellancy of variable density assessment printing ink image, and carry out classification by following A-C.
A: do not observe variation basically.
B: observe density and reduce.
B: observe density and obviously reduce.
The image that forms on the common paper that is used for PPC is carried out identical test.
4) light fastness
According to identical testing method and the staging hierarchy in embodiment 1, used.
5) ozone resistants
It is the chamber 7 days of 0.5ppm that recording picture is placed concentration of ozone gas.With with assessment light fastness identical mode, obtain to be exposed to the dyestuff retention after the ozone.(OZG-EM-01 derives from Applics Co., Ltd.) sets the ozone concn in the described chamber to utilize the ozone gas monitor.Each measurement point dyestuff retention be 80% or higher image be chosen as the A level.At one or two of three measurement point, the dyestuff retention is lower than 80% image and is chosen as the B level.All be lower than 80% image at each measurement point dyestuff retention and be chosen as the C level.
Table 16
Sample Dyestuff Tone Paper independence Water-repellancy Light fastness Ozone resistants
The photograph glossy paper Common paper
??I ????2-17 ??A ??A ??A ??A ??A ??A
??J ????2-18 ??A ??A ??A ??A ??A ??A
??K ????2-19 ??A ??A ??A ??A ??A ??A
??L ????2-20 ??A ??A ??A ??A ??A ??A
??M ????(a) ??A ??B ??B ??C ??C ??C
??N ????(b) ??C ??B ??B ??C ??B ??C
??O ????(c) ??B ??B ??B ??C ??B ??C
??P ????(d) ??A ??B ??B ??C ??A ??C
Table 16 shows, and is more more clear than the image that prints with ink composite M-P with the magenta color image of ink composite I-L printing.In addition, the image with ink I-L printing is being excellent aspect light fastness and the ozone resistants.
Embodiment 5
Utilize the ink composite I-L of preparation among the embodiment 4, on the photograph glossy paper (KA42OPSK derives from Seiko Epson) of ink jet printing head (PM-670C derives from Seiko Epson), carry out ink jet printing.The same satisfactory with regard to tone, paper independence, water-repellancy, light fastness and ozone resistants to the result who obtains among the assessment result of resulting image and the embodiment 4.
Embodiment 6
Each the ink jet printing head (BJ-F850 derives from Canon) of print cartridge among the ink composite I-L is equipped with in utilization, carries out ink jet printing on photograph glossy paper (GP-301 derives from Canon Inc.).With the mode identical resulting image is assessed with embodiment 4.The result is the same satisfactory with the result of acquisition in embodiment 4 and 5.
The invention provides a kind of new dyestuff, it has the absorption characteristic of excellent color rendition and enough light fastness, thermotolerance, wet fastness and to the patience of reactive gas in the environment as one of three primary colors; And provide the production method of described dyestuff.
In addition, the present invention also provides coloured composition, and said composition provides the tinting material of excellence aspect color harmony fastness of coloured image or widespread use, for example is used for the printing ink composition of ink jet printing; Be used for the printing ink sheet that heat transfer image forms material; The toning agent of electrophotography; The coloured composition that is used for the colour filter of LCD and CCD; With the dyeing solution that is used for textiles.
In addition, the present invention also provides inkjet ink composition, and this ink composite can form the image with the high light resistance of satisfied color harmony and gas of anti-environment activity the (particularly ozone).
Embodiment 7
1) compound 2-1-1's is synthetic:
2,6-two chloro-3-cyano group-4-picolines (10.0 grams, 53.4 mmoles) and 32.5 gram (240.3 mmole) 2 stirred 6 hours under 160 ℃ internal temperature.300 milliliters of ethyl acetate are added in the mixture, and continue to stir other 30 minutes.By removing by filter insoluble substance, and remove ethyl acetate by evaporation.Make resistates crystallization from hexane, thereby obtain the compound 2-1-1 of 13.4 grams, yield is 65%.
M/z (FAB-MS; The positive ion mode)=384
2) compound 2-1-11's is synthetic:
In the compound 2-1-1 of 10.0 grams (26.0 mmole), add the phosphoric acid of 25.0 grams and the Tripyrophosphoric acid of 25.0 grams, and under 160 ℃ internal temperature, mixture was stirred 6 hours.At room temperature, ethyl acetate is added into reaction mixture, and ethyl acetate solution is poured in 1 liter the frozen water, neutralize, carry out liquid-liquid separation then with sodium bicarbonate.Water washs organic layer and carry out drying on anhydrous sodium sulphate.By the filtering separation inorganics, and organic layer is concentrated.Hexane is added in the resistates so that the product that redeposition goes out to wish carries out recrystallize then from hexane/isopropyl alcohol (IPA) mixed solvent, is 95% compound 2-1-11 and obtain yield.
M/z (FAB-MS; The positive ion mode)=358
3) compound 2-1-2's is synthetic:
2,6-two chloro-3-cyano group-4-picolines (10.0 grams, 53.4 mmoles) and 58.9 gram (240.3 mmole) 4-n-octyl aniline stirred 6 hours under 160 ℃ internal temperature.300 milliliters of ethyl acetate are added in the mixture, and continue to stir other 30 minutes.By removing by filter insoluble substance, and remove ethyl acetate by evaporation.Hexane is added in the resistates, and passes through to filter the solid of collecting precipitation, thereby obtain the compound 2-1-2 of 27.8 grams (82%).
M/z (FAB-MS; The positive ion mode)=524
1H-NMR(CDCl 3)δ：0.881(t，J＝6.48Hz，6H，CH 3CH 2-)，1.275-1.314(m，20H，CH 3-C 5H 10-CH 2-)，1.570-1.613(m，4H，Ar-CH 2-CH 2-)，2.330(s，3H，-CH 3)，2.590(t，J＝7.44Hz，4H，Ar-CH 2-)，6.032(S，1H，-H)，6.547(s，1H，Ar-NH-)，6.842(s，1H，Ar-NH-)，7.127(d，J＝8.22Hz，4H，Ar-H)，7.202(d，J＝8.46Hz，2H，Ar-H)，7.436(d，J＝8.43Hz，2H，Ar-H).
Embodiment 8
1) azo-compound 2-2-1's is synthetic
Figure A0280800900861
Under 5 ℃ internal temperature, the mixture of the 5-amino-3-tertiary butyl-4-cyano pyrazole of 8 grams (48.7 mmole), 15 milliliters of concentrated hydrochloric acids and 15 milliliters of acetate and propionic acid 2/3 (by volume) is stirred.In 10 minutes, in this mixture, add the Sodium Nitrite of 3.36 grams (48.7 mmole) in batches, stirred then 10 minutes.Under 10 ℃ or lower internal temperature, resulting diazonium salt solution is dropped in 100 milliliters of pyridine solutions that contain 21.3 gram (40.6 mmole) compound 2-1-1.After being added dropwise to complete, under described temperature, this reaction mixture was stirred 30 minutes.Reaction mixture is poured in 1 liter of frozen water.By the azo-compound of suction filtration collecting precipitation, and carry out redeposition by IPA/ methanol mixed solvent.
The salt of wormwood of the 2-chloro benzothiazole of resulting azo-compound (15.4 gram, 40 mmoles), 17.0 grams (50 milliliters) and 5.5 grams are suspended in 100 milliliters the N,N-DIMETHYLACETAMIDE (DMAc), and when stirring in 100 ℃ of heating 1 hour.Reaction is cooled to room temperature with reaction mixture after finishing, and to the saturated aqueous solution that wherein adds 400 milliliters of sodium-chlor.Collect the throw out that so forms by suction filtration, and carry out recrystallize, thereby the azo-compound 2-2-1 of 25.6 grams (80%) is provided by acetonitrile.
λ max=532nm (dimethyl formamide (DMF) solution)
M/z (positive ion mode)=692
2) azo-compound 2-2-11's is synthetic
2-1) the synthetic method of using DMF to use alkali as coupling as the solvent and the sodium acetate of compound (2-I)
Under 5 ℃ internal temperature, mixture to the 5-amino-3-tertiary butyl-4-cyano pyrazole of 8 grams (48.7 mmole), 15 milliliters of concentrated hydrochloric acids and 15 milliliters of acetate/propionic acid 2/3 (by volume) stirs, and in 10 minutes, restrain the Sodium Nitrite of (48.7 mmole) to wherein dripping 3.36, and then carry out 10 minutes stirring in batches.Under 10 ℃ or lower internal temperature, resulting diazonium salt solution is dropped to 21.3 gram (40.6 mmole) compound 2-1-1 and 50.0 gram sodium acetates in the solution of 200 milliliters of mixed solvents (100 milliliters of DMF and 100 milliliters of acetate/propionic acid=2/3 are by volume).After being added dropwise to complete, under described temperature, this reaction mixture was stirred 30 minutes, and pour in 1 liter the frozen water.Collect sedimentary azo-compound like this by suction filtration, and in IPA/ methyl alcohol, carry out redeposition.
With 22.4 gram (40 mmole) resulting azo-compounds, the salt of wormwood of 17.0 gram (50 milliliters) 2-chloro benzothiazoles and 5.5 grams is suspended among 100 milliliters of DMAc, and heats 1 hour in 100 ℃ when stirring.Reaction is cooled to room temperature with reaction mixture after finishing, and to the saturated aqueous solution that wherein adds 400 milliliters of sodium-chlor.Collect the throw out that so forms by suction filtration, and carry out recrystallize, thereby the azo-compound 2-2-11 of 26.3 grams (82%) is provided by acetonitrile.
λ max=558nm (DMF solution), m/z (positive ion mode)=802
2-2) acetate/propionic acid is as the solvent of compound (2-I) and the triethylamine synthetic method as alkali
Prepare diazonium salt solution with the mode identical with above-mentioned (2-1).Under 10 ℃ or lower internal temperature, resulting diazonium salt solution dropped to the compound 2-1-11 of 21.3 grams (40.6 mmole) and be dissolved in 100 milliliters of triethylamines in 330 milliliters of acetate/propionic acid (2/3 by volume) mixed solvent.After being added dropwise to complete, under described temperature, this reaction mixture being stirred 30 minutes, and pour in the HCl aqueous solution of 1N.Collect sedimentary azo-compound like this by suction filtration, and in IPA/ methyl alcohol, carry out redeposition.
With with top (2-1) identical mode, utilize the 2-chloro benzothiazole to make resulting azo-compound heteroarylization, thus obtain 22.5 the gram (70%) azo-compound 2-2-11.
λ max=558nm (DMF solution), m/z (positive ion mode)=802
2-3) with pyridine as the solvent of compound (2-I) and the synthetic method of alkali
Prepare diazonium salt solution with the mode identical with above-mentioned (2-1).Under 10 ℃ or lower internal temperature, resulting diazonium salt solution is dropped in 60 milliliters of pyridine solutions that contain 21.3 gram (40.6 mmole) compound 2-1-11.After being added dropwise to complete, under described temperature, this reaction mixture being stirred 30 minutes, and pour in the HCl aqueous solution of 1N.Collect sedimentary azo-compound like this by suction filtration, and in IPA/ methyl alcohol, carry out redeposition.
With with top (2-1) identical mode, utilize the 2-chloro benzothiazole to make resulting azo-compound heteroarylization, thus obtain 29.8 the gram (93%) azo-compound 2-2-11.
λ max=558nm (DMF solution), m/z (positive ion mode)=802
By synthetic method (2-1), (2-2) and contrast (2-3) as can be seen, when when synthesizing, going out azo-compound of the present invention with higher produced in yields according to method (2-3).For better understanding, the reaction result of embodiment 8 is listed among the table 2-6.
Table 2-6
Synthesis step Productive rate (%)
????(2-1) ????82
????(2-2) ????70
????(2-3) ????93
Embodiment 9
1) azo-compound 2-3-1's is synthetic
Under 0 ℃ or lower internal temperature, 5-amino-4-cyano group-3-methyl isothiazole (0.25 gram, 1.8 mmoles), 1.2 milliliters of acetate and 1.8 milliliters of propionic acid are stirred, and to wherein adding 0.6 gram (1.98 mmole), 45% nitrosyl-sulfuric acid.Under described temperature, mixture was stirred 30 minutes, thus the preparation diazonium salt.In an independent flask, sodium acetate, 13.5 milliliters dimethyl formamide and 6 milliliters the ethyl acetate of compound 2-1-1, the 2.4g of 0.54 gram (1.5 mmole) stirred, and be cooled to 0 ℃ or lower internal temperature.Diazonium salt is added in this solution, and under described temperature, mixture was stirred 2 hours.In this reaction mixture, add 30 milliliters of saturated sodium-chloride water solutions, and collect formed throw out by suction filtration.By silica gel column chromatography (hexane/ethyl acetate) coarse crystallization is purified, thus obtain 0.05 the gram (55%) azo-compound 2-3-1.
λ max=529nm (DMF solution), m/z (FAB-MS; The negative ion mode)=509
Embodiment 10
With the compound of the present invention shown in the synthetic following table 2-7 of the mode identical with embodiment 7, and according to the azo-compound shown in the synthetic table of the method identical with embodiment 8 or 9 2-7.
The tone assessment:
Each azo-compound and the comparative dye 2-1 to 2-4 as follows that utilize compound of the present invention to make are dissolved among the DMF, regulator solution concentration, when utilizing UV spectrometer that Shimadzu company provides to measure with box lunch, during λ max in the magenta zone, absorbancy is 1.000.Utilize the UV spectrum of identical each solution of device measuring, and obtain the half-value wide (the absorption bandwidth when 0.500 absorbancy) in the magenta zone.Carry out following evaluation to the half value that so calculates is wide.
A...75 nanometer or narrower
The B...76-85 nanometer
The C...86-95 nanometer
D...96 nanometer or wideer
Gained the results are shown among the table 2-7.
Comparative dye 2-1:
Comparative dye 2-2
Comparative dye 2-3
Comparative dye 2-4:
Figure A0280800900931
Table 2-7
The compounds of this invention Synthesis step Azo-compound Productive rate (%) ???λmax/DMF Half value wide (nm) Assessment result Explain
????2-1-1 Embodiment 8 (2-3) ????2-2-1 ??80 ???532 ????80 ??A The present invention
????2-1-4 Embodiment 8 (2-3) ????2-2-4 ??67 ???554 ????84 ??A The present invention
????2-1-6 Embodiment 8 (2-3) ????2-2-6 ??69 ???552 ????83 ??A The present invention
????2-1-11 Embodiment 8 (2-3) ????2-2-11 ??93 ???545 ????83 ??A The present invention
????2-1-12 Embodiment 8 (2-3) ????2-2-12 ??73 ???543 ????91 ??B The present invention
????2-1-23 Embodiment 8 (2-3) ????2-2-23 ??85 ???556 ????83 ??A The present invention
????2-1-24 Embodiment 8 (2-3) ????2-2-24 ??68 ???565 ????82 ??A The present invention
????2-1-1 Embodiment 9 ????2-3-1 ??55 ???529 ????81 ??A The present invention
????- - Dyestuff 2-1 ??72 ???540 ????95 ??C Contrast
????- - Dyestuff 2-2 ??71 ???560 ????111 ??D Contrast
????- - Dyestuff 2-3 ??57 ???510 ????101 ??D Contrast
????- - Dyestuff 2-4 ??60 ???523 ????107 ??D Contrast
By table 2-7 as can be seen, demonstrated the comparison absorption band narrower by the azo-compound that utilizes compound of the present invention, and half value is wide narrower than dyestuff.
The invention provides a kind of new compound, can provide azo-compound with the wide sharp absorption characteristic of excellent color rendition and narrow half value as this compound of tricolor dye.In addition, the present invention also provides the high yield production method of described azo-compound.
As previously mentioned, each that will require foreign priority at this especially the full content of state's patent application be incorporated herein by reference.

Claims (13)

1. compound by following formula (I) expression:
R wherein 1' expression hydrogen atom, alkyl, cycloalkyl, aralkyl, aryl, heterocyclic radical or acyl group, wherein, each group can have substituting group; R 2' expression hydrogen atom, halogen atom or cyano group; R 3' expression hydrogen atom, alkyl, cycloalkyl, aralkyl, thiazolinyl, aryl, heterocyclic radical, carboxyl or sulfo group, wherein each group can have substituting group; R 4', R 5', R 6' and R 7' represent hydrogen atom, alkyl, cycloalkyl, aralkyl, thiazolinyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group, carboxyl, sulfo group or formamyl independently of one another, wherein each group can have substituting group, and precondition is R 4' and R 5' do not represent hydrogen atom simultaneously, and R 6' and R 7' do not represent hydrogen atom simultaneously; And A 1' and A 2' expression-CR=or nitrogen-atoms separately, precondition is A 1And A 2Do not represent nitrogen-atoms simultaneously, wherein R represents hydrogen atom or substituting group.
2. compound by following formula (2-I) expression:
Figure A0280800900022
Wherein, A 1Expression-CR 1=or nitrogen-atoms, A 2Expression-CR 2=or nitrogen-atoms, precondition is A 1And A 2Do not represent nitrogen-atoms simultaneously; R 6And R 7One of at least expression aryl or heterocyclic radical, another expression hydrogen atom, aliphatic group, aryl, heterocyclic radical, acyl group, carbalkoxy, aryloxy carbonyl, sulfamyl, wherein each group can have substituting group; G, R 1And R 2Represent hydrogen atom separately; halogen atom; aliphatic group; aryl; heterocyclic radical; cyano group; carboxyl; formamyl; carbalkoxy; aryloxy carbonyl; acyl group; hydroxyl; alkoxyl group; aryloxy; siloxy-; acyloxy; carbamoyloxy; heterocyclic oxy group; alkoxyl group carbonyl oxygen base; aryloxy carbonyl oxygen base; the amino that alkyl or aryl or heterocyclic radical replace; amide group; urea groups; sulfamoylamino group; alkoxycarbonyl amino; aryloxycarbonyl amino; alkyl sulfonyl amino; Arenesulfonyl amino; nitro; alkylthio; arylthio; the heterocycle sulfenyl; alkyl sulphonyl; aryl sulfonyl; alkyl sulphinyl; aryl sulfonyl kia; sulfamyl or sulfo group; wherein each group can have substituting group, and precondition is to work as A 1And A 2Expression-CR respectively 1=and-CR 2In=time, G is not the amino of alkyl-replacement; Or R 1And R 6Together, or R 6And R 7Form 5-unit or 6-unit ring together respectively.
3. according to the compound of claim 1, wherein, the compound of structural formula (I) expression is represented by formula (I-R1):
Figure A0280800900031
Wherein, R 1', R 2', R 4', R 5', R 6', R 7', A 1' and A 2' as definition in the structural formula (I); And the R of structural formula (I-R1) 3" expression alkyl, cycloalkyl, aralkyl, thiazolinyl, aryl, heterocyclic radical, carboxyl or sulfo group.
4. according to the compound of claim 3, wherein the compound of structural formula (I-R1) expression is represented by formula (I-R2):
Figure A0280800900032
Wherein, R 1', R 2', R 3＂, R 5', R 6', R 7', A 1' and A 2' as definition in the structural formula (I-R1); And the R of structural formula (I-R2) 4" expression replacement or unsubstituted alkyl, replacement or unsubstituted cycloalkyl, replacement or unsubstituted aralkyl, replacement or unsubstituted thiazolinyl, replacement or unsubstituted aryl, replacement or unsubstituted heterocyclic.
5. according to the compound of claim 3, wherein the compound of structural formula (I-R1) expression is represented by formula (I-R3):
Figure A0280800900041
Wherein, R 1', R 2', R 3", R 5', R 6', R 7', A 1' and A 2' as definition in the structural formula (I-R1).
6. according to the compound of claim 3, wherein the compound of structural formula (I-R1) expression is represented by formula (I-R4):
Wherein, R 1', R 2', R 3", A 1' and A 2' as definition in the structural formula (I-R1); And R (I-R4) 4_, R 5", R 6" and R 7" represent hydrogen atom, alkyl, cycloalkyl, aralkyl, thiazolinyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group or formamyl separately.
7. according to the compound of claim 1, wherein the compound of structural formula (I) expression is represented by formula (I-H1):
Figure A0280800900051
Wherein, R 1', R 2', R 4', R 5', R 6', R 7', A 1' and A 2' as definition in the structural formula (I).
8. according to the compound of claim 7, wherein the compound of structural formula (I-H1) expression is represented by following formula (I-H2):
In the formula, R 1', R 2', R 6', A 1' and A 2' as definition in the structural formula (I-H1); And the R of structural formula (I-H2) 5_ and R 7_ represent alkyl, cycloalkyl, aralkyl, thiazolinyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group, carboxyl, sulfo group or formamyl independently of one another, wherein each group can have substituting group.
9. according to the compound of claim 2, wherein the compound of structural formula (2-I) expression is represented by following formula (2-II):
Wherein, R 1, R 2, R 6And R 7As definition in the structural formula (2-I); And R 4And R 5One of at least expression aryl or heterocyclic radical, and another expression hydrogen atom, aryl, heterocyclic radical, acyl group, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkylsulfonyl or sulfamyl, wherein R 1, R 2, R 4, R 5And R 6Separately substituting group can be arranged.
10. production method by the compound of following structural formula (I-R1) expression:
Wherein, R 1' expression hydrogen atom, alkyl, cycloalkyl, aralkyl, aryl, heterocyclic radical or acyl group, wherein each group can have substituting group; R 2' expression hydrogen atom, halogen atom or cyano group; R 3" expression alkyl, cycloalkyl, aralkyl, thiazolinyl, aryl, heterocyclic radical, carboxyl or sulfo group, wherein each group can have substituting group; R 4', R 5', R 6' and R 7' represent hydrogen atom, alkyl, cycloalkyl, aralkyl, thiazolinyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group, carboxyl, sulfo group or formamyl independently of one another, wherein each group can have substituting group, and precondition is R 4' and R 5' do not represent hydrogen atom simultaneously, and R 6' and R 7' do not represent hydrogen atom simultaneously; A 1' and A 2' expression replaces or unsubstituted carbon atom or nitrogen-atoms separately, and precondition is A 1' and A 2' do not represent nitrogen-atoms simultaneously,
Described method comprises the steps:
(a) amino-pyrazol-derivatives and diazo reagent by structural formula (II) expression are reacted, so that form diazonium salt;
Figure A0280800900062
Wherein, R 1' and R 2' as definition in the structural formula (I-R1);
(b) make diazonium salt and the coupling component reaction of representing by structural formula (III), with the compound of formation by structural formula (I-H1) expression,
Figure A0280800900071
Wherein, R 4', R 5', R 6', R 7', A 1' and A 2' as definition in the structural formula (I-R1),
Wherein, R 1', R 2', R 4', R 5', R 6', R 7', A 1' and A 2' as definition in the structural formula (I-R1); With
(c) compound that makes structural formula (I-H1) expression in the presence of alkali with alkylating reagent, aromatic yl reagent-ing or heteroaryl reagent react, or comprise the steps:
Water soluble group is introduced in the compound of representing by structural formula (I-R4) by cationoid reaction:
Wherein, R 1', R 2', R 3", A 1' and A 2' as definition in the structural formula (I-R1); And R (I-R4) 4_, R 5", R 6" and R 7" represent hydrogen atom, alkyl, cycloalkyl, aralkyl, thiazolinyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group or formamyl separately.
11. production method by the compound of following structural formula (I-R2) expression:
Figure A0280800900081
In the formula, R 1' expression hydrogen atom, alkyl, cycloalkyl, aralkyl, aryl, heterocyclic radical or acyl group, wherein each group can have substituting group; R 2' expression hydrogen atom, halogen atom or cyano group; R 3" expression alkyl, cycloalkyl, aralkyl, thiazolinyl, aryl, heterocyclic radical, carboxyl or sulfo group; R 4" expression replacement or unsubstituted alkyl, replacement or unsubstituted cycloalkyl, replacement or unsubstituted aralkyl, replacement or unsubstituted thiazolinyl, replacement or unsubstituted aryl or replacement or unsubstituted heterocyclic; R 5', R 6' and R 7' represent hydrogen atom, alkyl, cycloalkyl, aralkyl, thiazolinyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group independently of one another, carboxyl, sulfo group or formamyl, wherein each group can have substituting group, and precondition is R 6' and R 7' do not represent hydrogen simultaneously; And A 1' and A 2' expression independently of one another replaces or unsubstituted carbon atom or nitrogen-atoms, and precondition is A 1' and A 2' do not represent nitrogen-atoms simultaneously,
Described method comprises the steps:
Compound and alkylating reagent, aromatic yl reagent-ing or the heteroaryl reagent of (I-H1) expression are reacted under oxygen free condition,
R in the formula 1', R 2', R 5', R 6', R 7', A 1' and A 2' as definition in the structural formula (I-R2); And R 4' expression hydrogen atom, alkyl, cycloalkyl, aralkyl, thiazolinyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group, carboxyl, sulfo group or formamyl, wherein each group can have substituting group, and precondition is R 4' and R 5' do not represent hydrogen atom simultaneously,
Or comprise the steps:
Make compound and alkylating reagent, aromatic yl reagent-ing or the heteroaryl reagent react of structural formula (I-H2) expression,
Figure A0280800900091
R wherein 1', R 2', R 6', A 1' and A 2' as definition in the structural formula (I-R2); And the R of structural formula (I-H2) 5_ and R 7_ represent alkyl, cycloalkyl, aralkyl, thiazolinyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group, carboxyl, sulfo group or formamyl independently of one another, wherein each group can have substituting group;
With the compound of formation by following formula (I-R3) expression,
The R of structural formula (I-R3) wherein 1', R 2', R 3＂, R 5', R 6', R 7', A 1' and A 2' as definition in the structural formula (I-R2); With
Make compound by structural formula (I-R3) expression under oxygen free condition with alkylating reagent, aromatic yl reagent-ing or heteroaryl reagent react.
12. the production method of an azo-compound, it comprises that compound that makes claim 2 and the diazonium salt that forms by diazo reagent react.
13. the production method of an azo-compound, it compound that comprises structural formula (2-II) expression that makes according to claim 9 reacts with the diazonium salt that forms by diazo reagent.
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US20070173641A1 (en) 2007-07-26
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US20040122219A1 (en) 2004-06-24

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